Gallbladder and Liver Therapy 1

Gallbladder and Liver Therapy

Géza Csomós, Hamburg, Federal Republic of Germany (Chaps. 1 and 3)
Ulrich Leuschner, Johann Wolfgang Goethe Universität, Frankfurt, Federal Republic of Germany (Chap. 2)

1. Choleretics . . . . . . . . . . . . . . . . 2 2.5. Direct Dissolution of Bile Duct

1.1. Natural Products . . . . . . . . . . . . 2 Stones . . . . . . . . . . . . . . . . . . . . 9
1.2. Synthetic Products . . . . . . . . . . . 3 2.6. Critical Assessment of Chemical
1.2.1. Benzyl Alcohol Derivatives . . . . . . 3 Stone Dissolution . . . . . . . . . . . . 9
1.2.2. Cinnamic Acid Derivatives . . . . . . . 3 3. Liver Therapeutics . . . . . . . . . . . 10
3.1. Introduction . . . . . . . . . . . . . . . 10
1.2.3. Miscellaneous Synthetic Choleretics . 4
3.2. Therapeutic Agents . . . . . . . . . . . 11
2. Dissolution of Gallstones . . . . . . . 6 3.2.1. Inhibitors of Viral Nucleic Acid Syn-
2.1. Gallstone Pathophysiology . . . . . . 6 thesis . . . . . . . . . . . . . . . . . . . . 11
2.2. Oral Dissolution of Gallbladder 3.2.2. Bile Salts used for Primary Biliary
Stones with Bile Acids . . . . . . . . . 6 Liver Disease . . . . . . . . . . . . . . . 12
2.3. Direct Percutaneous – Transhepatic 3.2.3. Natural Substances . . . . . . . . . . . . 12
Lysis (PTL) of Gallbladder Stones . 8 3.2.4. Miscellaneous Substances . . . . . . . 14
2.4. Oral Litholysis after Extracorporeal 3.2.5. Antifibrinogenic Drugs . . . . . . . . . 17
Shock-Wave Lithotripsy (ESWL) . 8 4. References . . . . . . . . . . . . . . . . . 18

Abbreviations: PTL percutaneous – transhepatic ly-

sis
ALT alanine aminotransferase
RNA ribonucleic acid
ara-A 9-β-d-arabinofuranosyladenine
urso ursodeoxycholic acid
ara-AMP 9-β-d-arabinofuranosyladenine
5-monophosphate This article is divided into three chapters
AST aspartate aminotransferate that deal with substances that increase bile flow
BSP bromsulphalein (choleretics, Chap. 1), the dissolution of gall-
cheno chenodeoxycholic acid stones in the gallbladder and bile duct (Chap.
DNA deoxyribonucleic acid 2), and drugs used for liver therapy (Chap. 3).
EDTA ethylenediaminetetraacetic acid
EPL essential phospholipids
ESWL extracorporeal shock-wave 1. Choleretics
lithotripsy
GLDH glutamate dehydrogenase Although the gallbladder is not one of the most
GOT (AST) glutamic – oxalacetic transami- vital organs of the human body, it causes many
nase subjective complaints and objective changes, so
GPT (ALT) glutamic – pyruvic transami- that it continues to be a subject of great interest
nase in both research and medicine. Numerous sub-
γ-GT γ-glutamyltransferase stances have been tested in animals with a view
HBV hepatitis B virus to stimulating bile flow or inhibiting lithogenesis
HMG-CoA β-hydroxy-β-methylglutaryl- (i.e., stone formation). Stimulation of bile flow
coenzyme A has been attributed to several substances [1].
MAST microprocessor-assisted solvent A cholagogue is a substance that in-
transfer system creases bile flow. Cholagogues may be either
MTBE methyl tert-butyl ether choleretics, which stimulate secretion of bile by
PTC percutaneous – transhepatic the liver, or cholekinetics, which lead to empty-
cholangiography ing of the gallbladder [2].

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 143
2 Gallbladder and Liver Therapy

The major constituents of bile are the surface-
active bile acid salts; other components in-
clude cholesterol, phospholipids, bilirubin, mu-
cus, and inorganic salts. Bile is produced in
liver cells and secreted into the bile ducts. It
then passes through a shunt into the gallblad-
der, where it is concentrated to about one-tenth
of its original volume. After ingestion of food,
the gallbladder contracts and forces the concen-
trated bile into the duodenum via the common
bile duct [3].
On the average, about 500 – 600 mL of bile
is produced daily. Secretion of water and elec-
trolytes into the bile duct system is stimulated
by
1) secretin,
2) the autonomous nervous system,
3) changes in pressure in the bile duct, and
4) changes in the flow of blood through the liver.
The most important function of bile is the di-
gestion of fats: it emulsifies ingested fats and
activates pancreatic lipase.
Cholagogic drugs have not become estab-
lished in English-speaking and Scandinavian
countries, where they are viewed rather skep-
tically by the medical field. However, in other
European countries where medicine is more in-
clined to speculation, these substances still play
a surprisingly important role. Many of them have
been tested only in animals, and their effects
were found to be species dependent. However,
results obtained in animal experiments cannot
be extrapolated to humans, and investigations
on humans have generally used unsatisfactory
methods (e.g., duodenal probes). When reliable
methods were employed to test choleretics in
humans, only the bile acid preparations were
found to be effective [4]. The choleresis ob-
served on administration of bile acids involves
an increased secretion of water and electrolytes
(i.e., hydrocholeresis) and can also be observed
during spontaneous fluctuations of bile secre-
tion or after intake of food. True choleresis,
i.e., increased secretion of bile-specific sub-
stances, cannot be induced by drugs. In addi-
tion to these drawbacks, unlimited therapeutic
use of choleretics cannot be recommended for
any single disease of the digestive tract [5].
Substances native to the body (bile prepara-
tions), plant drugs, and synthetic compounds are
prescribed as therapeutic choleretics. However,
they must be viewed in light of the above state-
ments.
1.1. Natural Products
Bile Preparations. Substances native to the
body are supplied as choleretics in the form
of bile preparations and their derivatives. They
stimulate the secretion of bile in the liver. The ac-
tive agents in these preparations are sodium gly-
cocholate [ 475-31-0] and sodium taurocholate
[81-24-3]. ( Glycocholic and taurocholic acids
are formed by conjugation of the bile acid cholic
acid with glycine or taurine, respectively.) Fur-
ther choleretics are the naturally occurring bile
acids (e.g., cholic and deoxycholic acids) and
dehydrocholic acid, which is obtained by oxi-
dizing cholic acid .
Deoxycholic acid [83-44-3]: 3,12-di-
hydrocholanic acid
Cholic acid [81-25-4]: 3,7,12-trihydroxychola-
nic acid
Dehydrocholic acid [81-23-2]: 3,7,12-trioxo-
cholanic acid
Trade Names. Decholin (Casella-Riedel,
Frankfurt), Agicholit (Brunnengräber, Lübeck),
Chol-Arbuz (Schwag, München), Gallo Sanol
(Sanol, Monheim).
Plant Drugs. Drugs obtained from plants
constitute the largest number of cholagogues and
are used in tea mixtures or other preparations.
In addition, special products also contain bile
acids, spasmolytic agents, and substances that
stimulate digestion.
The most frequently used medicinal herbs
are Berberis vulgaris (barberry), Chelidonium
majus (celandine), different types of turmeric,
Cynara scolymus (artichoke), Peumus boldus (a
South American plant), Mentha piperita (pep-
permint), Raphanus sativus (black radish), and

Taraxacum officinale (dandelion). Very few of
the drugs extracted from these plants have been
investigated chemically or pharmacologically.
The active ingredients of turmeric and artichoke
are described in Sections 1.2.1 and 1.2.2.
Trade Names. Cholagogum capsules
(Nattermann, Köln), Cholagutt-A (Albert-
Roussel, Wiesbaden), Choleodoron (Weleda,
Schwäbisch Gmünd), Galleb (Hover, Neuss),
Heparaxal (Roland, Essen), Bilicura (Müller,
Göppingen), Hepata (Madaus, Köln).
1.2. Synthetic Products
1.2.1. Benzyl Alcohol Derivatives
The choleretic ingredient of the plant drug
turmeric (Curcuma ) is p-tolylmethylcarbinol.
Synthetic choleretics based on this struc-
ture have been developed by lengthening the
aliphatic carbon chain or modifying the sub-
stituents of the aromatic ring. Reaction of the
carbinol with a dicarboxylic acid gives a mo-
noesterified acid whose sodium and dietha-
nolamine salts are water-soluble [6]. Among the
large number of compounds synthesized, the fol-
lowing are of practical importance.
1-Phenylpropanol [93-54-9], C9 H12 O,
M r 136.19, bp (101.3 kPa) 219 ◦ C.
1-Phenylpropanol is obtained (1) by reaction
of ethylsodium with benzaldehyde in toluene
and decomposition of the reaction product with
water or (2) from benzaldehyde and ethylmag-
nesium halogenides [5]. Its toxicity is low; the
oral LD50 in rats is 1500 mg/kg [1], [2], [6].
Trade Name. Felicur (Asche, Hamburg).
1-Phenylpentanol [583-03-9], fenipen-
tol, C11 H16 O, M r 164.25, bp (1.62 kPa)
123 – 124 ◦ C, is obtained by condensing styrene
oxide with ethyl acetoacetate to form α-aceto-
γ-phenyl- γ -butyrolactone. Decarboxylation
and Wolff –Kishner reduction of this compound
give 1-phenylpentanol [7] (see next page, on
top).
Gallbladder and Liver Therapy 3
The oral LD50 in mice is 3.10 g/kg [3], [8],
[9].
Trade Name. Cholipin (Thomae, Biberach).
1.2.2. Cinnamic Acid Derivatives
Cynarin [30964-13-7], 1,4-bis(3,4-di-
hydroxycinnamoyloxy)-3,5-dihydroxycyclo-
hexanecarboxylic acid, C25 H24 O12 , M r 516.44,
mp 225 – 227 ◦ C.
For structural elucidation and synthesis, see
[10]. Cynarin is a cinnamic acid derivative found
in artichokes. It possesses choleretic properties,
lowers the cholesterol level in blood, and is a
mild diuretic [11].
Toxicity is low, although use of high dosages
for long periods can cause a pathological de-
crease in liver and kidney function [12].
Trade Name. Cynarix (Sagitta, Feldkirchen).
Dimecrotic acid [7706-67-4],
2,4-dimethoxy-β-methylcinnamic acid.
Dimecrotic acid is a choleretic agent with spas-
molytic properties. It is obtained by reaction of
resorcinol with acetoacetate to give 4-methyl-
7-hydroxycoumarin. Treatment with dimethyl
sulfate and sodium carbonate gives the final
product [13].
Trade Name. Hepadial (Lab. Biocodex, Mon-
trouge Cedex).
1.2.3. Miscellaneous Synthetic Choleretics
Cyclobutyrol [512-16-3], α-ethyl-1-
hydroxycyclohexaneacetic acid, C10 H18 O3 ,
M r 186.24, mp 81 – 82 ◦ C; sodium salt,
mp 299 – 300 ◦ C.
4 Gallbladder and Liver Therapy

is a chemotherapeutic agent used against var-

ious cocci, Escherichia coli, Proteus vulgaris,
and other pathogenic agents involved in inflam-
mation of the biliary tract and the gallbladder.
The nicotinamide moiety is responsible for its
Cyclobutyrol is a choleretic without cholekinetic
choleretic and spasmolytic action [18].
action [14]. The ethyl ester is obtained via the
Trade Name. Bilamid (Cilag-Chemie, Alsbach-
Reformatsky reaction by heating cyclohexanone
Bergstraße).
with ethyl α-bromobutyrate in anhydrous ben-
zene in the presence of zinc oxide. The ester is
saponified to give the product [15]. Anethole trithione [532-11-6], 5-(4-
Trade Name. Hebucol (Logeais, Issy-les- methoxyphenyl)-3H-1,2-dithiole-3-thione,
Moulineaux). C10 H8 OS3 , M r 240.36, mp 111 ◦ C, is obtained
as follows [19]:
β-(1-Methoxy-4-naphthoyl)propionic
acid [3562-99-0], C15 H14 O4 , M r 258.26,
mp 172 – 173 ◦ C.

This substance proved to be the most effective

compound in tests carried out on ketocarboxylic
acids derived from naphthalene. It is obtained by
reaction of 1-methoxynaphthalene with succinic
anhydride in the presence of Friedel – Crafts cat-
Anethole trithione has choleretic and mild
alysts [16].
cholekinetic properties. It also increases the for-
Trade Names.Magnesium salts: Icteryl, Hepa-
mation and excretion rates of urea and thus has
lande (Delalande, Courbevoie).
a diuretic effect [20].
Trade Name. Mucinol (Plantorgan, Bad Zwis-
N-(Hydroxymethyl)nicotinamide
chenahn).
[3569-99-1], C 7 H8 N2 O2 , M r 152.15,
mp 141 – 142 ◦ C.
Azintamide [1830-32-6], 2-[(6-chloro-
3-pyridazinyl)thio]- N,N-diethylacetamide,
C10 H14 ClN3 OS, M r 259.77, mp 97 – 98 ◦ C,
can be obtained by treatment of 3,6-di-
chloropyridazine with hydrogen sulfide and sub-
N-(Hydroxymethyl)nicotinamide is obtained sequent reaction of the 6-mercapto compound
by reaction of nicotinamide with formaldehyde with N,N-diethylchloroacetamide:
in the presence of potassium carbonate [17]. It

Azintamide can also be obtained by reacting
the acetyl chloride derivative of the mercapto
compound with diethylamine [21]:
Azintamide is highly effective and is quickly ab-
sorbed from the intestine. It increases bile flow
and has neither an excitatory nor an inhibitory
effect on the central nervous system [22].
Trade Name. Orgallin (Hormon Chemie,
München).
Hymecromone [90-33-5], 7-hydroxy-
4-methylcoumarin, C10 H8 O3 , M r 176.16,
mp 194 –195 ◦ C.
Hymecromone is obtained by reaction of resor-
cinol with acetoacetate [23]. It is a spasmolytic
agent that selectively acts on the bile ducts,
particularly on Oddi’s sphincter. Sphincter di-
astole is lengthened, and bile flow into the in-
testine increases. Hymecromone also possesses
choleretic properties [24].
Trade Name. Cantabilin (Medica, Lipha, Lyon).
Moquizone [19395-58-5], 2,3-dihydro-1-
(4-morpholinylacetyl)-3-phenyl-4(1 H)-quina-
zolinone, C20 H21 N3 O3 , M r 351.41, mp 135 –
137 ◦ C; hydrochloride, mp 210 – 214 ◦ C.
Gallbladder and Liver Therapy 5
Moquizone is synthesized by reacting 2,3-di-
hydro-4(1 H)-quinazolinone with chloroacetyl
chloride and subsequently with morpholine [25].
Moquizone exhibits choleretic effects in ani-
mal experiments [26].
Trade Name. Peristil (Recordati, Milano).
2. Dissolution of Gallstones
Chemical gallstone dissolution (litholysis) can
be achieved by four methods:
1) oral therapy with the bile acids chenodeoxy-
cholic or ursodeoxycholic acid,
2) direct percutaneous – transhepatic lysis with
methyl tert-butyl ether,
3) oral litholysis after extracorporeal shock-
wave lithotripsy,
4) direct dissolution of bile duct stones via a
nasobiliary tube or T-tube.
2.1. Gallstone Pathophysiology
Classification of Gallstones. Gallstones
consist of a mixture of cholesterol, pigments,
calcium bilirubinate, inorganic calcium salts,
electrolytes, heavy metals, fatty acids, mucins
and mucoproteins. The predominant component
in the stone provides its name. The most com-
mon gallstone found in patients in industrialized
countries is the cholesterol stone; pigment stones
occur less frequently. Cholesterol stones con-
tain at least 75 % cholesterol, whereas pigment
stones contain no more than 25 % cholesterol
[27]. An interesting pigment stone is the black
pigment stone; little is known about its patho-
genesis and composition. Concretions consist-
ing predominatly of fatty acids are extremely
rare. The composition, incidence, and physi-
ological sites of occurrence of gallstones are
summarized in Table 1.
6 Gallbladder and Liver Therapy
Table 1. Classification, incidence, and localization of human gallstones

Type of stone Composition Prevalence Localization

Cholesterol stone
70 % cholesterol, 70 – 90 % of all gallbladder; in 15 %

pigments, calcium gallbladder of patients, gallbladder plus
salts, mucins, stones [28] common bile duct
proteins

Composition stone like cholesterol 20 %; higher in like cholesterol

(mixed stone) stones, but with older patients stones
significantly lower
cholesterol content
(30 – 70 %)

Calcium bilirubin- < 30 % cholesterol, 60 % of all common common bile duct;

ate stone (brown high calcium bilirubinate bile duct stones after rare in the gallbladder
pigment stone) content cholecystectomy

Black pigment black pigment, 5 – 30 % of all gallbladder gallbladder; rare in the

stone mucins, proteins stones [28] common bile duct

Stone Formation. Formation of cholesterol
stones is induced by a hepatic metabolic dis-
order. In the liver of gallstone carriers, the ac-
tivity of β-hydroxy-β-methylglutaryl coenzyme
A (HMG-CoA) reductase – the key enzyme of
cholesterol synthesis – is increased. In addi-
tion, 7-α-hydroxylase, which catalyzes one of
the steps in the conversion of cholesterol to bile
acids, is diminished [29]. This results in high se-
cretion of cholesterol and low secretion of bile
acids into bile. Bile acids are essential for the mi-
cellar dissolution of water-insoluble cholesterol.
Thus, when micellar capacity is exhausted by in-
creased cholesterol output, cholesterol precipi-
tates and forms cristals. A glycoprotein, proba-
bly secreted by the gallbladder mucosa, serves
as a nucleation factor in initial stone formation
[30]. Mucin production by the gallbladder wall
and also gallbladder function play an important
role in stone formation. Furthermore, stone for-
mation depends on the sex of the patient and is
affected by diet, body weight, race, and diseases
of the liver and the intestinal tract [30–33].
Little is known about the formation of black
pigment stones. Their incidence is higher in ur-
ban populations and in patients who consume
a protein-rich diet. Hemolytic diseases associ-
ated with a surplus of unconjugated bilirubin
are relevant. Brown calcium bilirubinate stones
in the billiary tree form after increased bacterial
deconjugation of bilirubinate – diglucuronide in
bile duct infections. Therefore, these stones are
found mostly after cholecystectomy or as a re-
lapsing (recurrent) stone after endoscopic papil-
lotomy. They often occur in rural populations
with a low-protein diet.
2.2. Oral Dissolution of Gallbladder
Stones with Bile Acids
Oral administration of the bile acids chen-
odeoxycholic acid [474-25-9] (cheno) or ur-
sodeoxycholic acid [128-13-2] (urso) is indi-
cated only in patients with cholesterol gallblad-
der stones. Chenodeoxycholic acid is given in
a dosage of 15 mg per kilogram body weight
daily. Dissolution rate is dose dependant and is
augmented by a low-cholesterol diet [34]. Urso
preparations are given in a daily dosage of 10 mg
per kilogram body weight daily. Higher doses
are of no avail [35].
Mode of Action of Bile Acids. Chen-
odeoxycholic acid acts by inhibiting HMG-CoA
reductase and the 7-α-hydroxylase in the liver
(cf. Section 2.1) [29]; this diminishes the secre-
tion of cholesterol and bile acid into bile. The
administered chenodeoxycholic acid is also se-
creted into bile, where it solubilizes the choles-
terol incorporated in the stones by means of
micelle formation.
Ursodeoxycholic acid has little influence,
if any, on HMG-CoA reductase and the
micellar dissolution of stone cholesterol. It
acts by forming cholesterol liquid crystals

(phospholipid – bile salt – cholesterol vesicles)
and inhibiting cholesterol reabsorption in the in-
testine [36], [37].
Cheno- and ursodeoxycholic acid act differ-
ently; both mechanisms are used for chemical
stone dissolution. Dosage reduction of the indi-
vidual bile acid is possible in combination ther-
apy [38] and diminishes their side effects, i.e., di-
arrhea and elevation of transaminases with chen-
odeoxycholic acid, or stone calcification with
ursodeoxycholic acid.
Patient Selection. Therapeutic success de-
pends largely on patient selection. Criteria for
successful treatment are
1) radiolucent cholesterol stones in the gall-
bladder,
2) gallbladder less than 50 % filled,
3) stone diameter ≤1.5 cm,
4) functioning gallbladder after stimulation,
5) patent (i.e., unobstructed) cystic duct,
6) patent common bile duct, and
7) patient compliance.
Contraindications for oral stone dissolution
are as follows:
1) pigment stones and calcified stones,
2) stone diameter >1.5 cm,
3) stones in the cystic duct or common bile
duct,
4) acute or chronic cholecystitis,
5) suspected bile duct carcinoma,
6) marked gallbladder septa,
7) acute or chronic liver disease,
8) chronic intestinal inflammation,
9) acute gastric or duodenal ulcer, and
10) frequent severe colics or constant pain.
Ultrasonic imaging reveals whether stones
are present. A subsequent X-ray shows ring-
shaped or totally calcified stones. Oral or intra-
venous cholecystography allows differentiation
between pigment and cholesterol stones and pro-
vides information regarding stone number, age,
and central spotlike calcifications.
According to [39], only 24 % of gallstone pa-
tients are suitable for conservative medical treat-
ment; a second study reports a figure of 59 %
[40]. This discrepancy is a result of the com-
position of the patient cohort: in the first study,
only patients with advanced gallstone disease
were examined; in the second study, early forms
of stone disease were investigated.
Gallbladder and Liver Therapy 7
Clinical Results. Complete stone dissolu-
tion is achieved with monotherapy (cheno:
15 mg kg−1 d−1 ; urso: 10 mg kg−1 d−1 ) in ca.
60 % of all patients treated (Table 2) [41–43].
Combination therapy (cheno + urso, half dosage
each) is reported to induce dissolution more
rapidly than monotherapy, according to a study
in 120 patients [38]. The therapeutic result de-
pends mostly on stone size and treatment time.
Small concretions of about 0.5 cm can be dis-
solved in 80 – 90 % of patients, but stones with a
diameter of 2 cm rarely dissolve [41], [42], [44].
The mean treatment time for stones up to 1.5-cm
diameter is 19 months [45].
About 40 % of successfully treated patients
experience stone recurrence [46]; these stones
are usually cholesterol stones that can be dis-
solved within a few months. Recently it has been
shown that the recurrent stone should be treated
immediately after its detection and not just after
colics or abdominal pain has developed. Using
this treatment scheme 80 – 90 % of the patients
remain stone free after 5 years.
2.3. Direct Percutaneous – Transhepatic
Lysis (PTL) of Gallbladder Stones
Cholesterol gallbladder stones were first dis-
solved with percutaneous – transhepatic lysis
(PTL) in 1985 [45]. Dissolution was per-
formed with 2 – 10 mL of methyl tert-butyl ether
[1634-04-4] (MTBE) which was instilled di-
rectly into the gallbladder and reaspirated ime-
diately. Treatment requires 1 – 2 d and produces
a few mild side effects (e.g., nausea, vomiting,
and mild upper abdominal pain) [47]. Leakage
of bile into the peritoneal cavity after withdrawal
of the perfusion catheter presents a certain risk.
The therapeutic success of PTL is greater than
90 %, at a cost of ca. 200 DM ($ 100) per patient
[48]. Further therapeutic results are summarized
in Table 3. MTBE-therapy is contraindicated by
the following:
1) calcified stones and pigment stones,
2) obstruction of the cystic duct,
3) acute or chronic cholecystitis,
4) small gallbladder bed area, and
5) gallbladder anomalies.
8 Gallbladder and Liver Therapy
Table 2. Gallstone dissolution in patients treated with chenodeoxycholic acid (cheno), ursodeoxycholic acid (urso), or cheno vs. urso.

Bile acid ∗ Patients Dosage Stone Patients with

−1 −1
No. Body weight, mg kg d No. Mean size, complete stone
kg (mean) cm2 dissolution, %

Cheno 28 65.4 15.0 8 4.9 60.7

Urso 135 63.8 11.3 12 4.0 62.2
Cheno vs. 20 60.9 15.8 cheno 8.5 1.1 61.0
urso 28 64.5 11.5 urso 17 0.3 85.0

∗ Patients were treated with Chenofalk and Ursofalk (Falk Pharma, Freiburg, Federal Republic of Germany).

2.4. Oral Litholysis after Extracorporeal 2.5. Direct Dissolution of Bile Duct
Shock-Wave Lithotripsy (ESWL) Stones

Extracorporeal shock-wave lithotripsy (ESWL) Bile duct stones are removed endoscopically in
is based on the concentration of an energy over 90 % of patients [50], [51]. Chemical disso-
wave produced by spark discharge to a radio- lution is seldom indicated [52]. For cholesterol
logically or sonographically localized gallblad- stones, 2 – 5 mL of glyceryl monooctanoate is
der stone [49]. However, because the result- infused via a T-tube or a nasobiliary tube into the
ing stone fragments remain in the gallbladder, bile ducts. Complete stone dissolution has been
ESWL is possible only in combination with achieved in 50 – 60 % of 600 patients treated.
oral litholysis; therefore, patients must be se- Side effects are epigastric pain and diarrhea. Av-
lected carefully (cf. Section 2.2). After approx- erage treatment time is three weeks. Methyl tert-
imately six months, the combination method butyl ether is not suitable (or only suitable in
ESWL – litholysis completely removes solitary the hands of an expert) for dissolution because
stones with a diameter of 2 cm in about 80 % of it flows into the intestine where it is reabsorbed
patients. Patients with three 1-cm stones become and has an anesthetizing effect (see also Table 3).
stone free after 18 months. Disadvantages of the Calcium bilirubinate concrements account
treatment are its very high cost (the gallstone for up to 60 % of all bile duct stones found
lythotriptor costs ca. 3.2×106 DM ≈ $ 2×106 ), after cholecystectomy and can be dissolved
and only three concretions can be fragmented in by perfusion with an alkaline, buffered ethyl-
any one patient. Furthermore, ESWL is unsuit- enediaminetetraacetate solution (10 – 15 mL/h)
able for calcified cholesterol and pigment stones. [53]. In vitro, this solution dissolves almost all
calcium bilirubinate stones and even black pig-
Table 3. Results of stone dissolution with MTBE – data from 21
European centres ment stones within 30 h [54]. The aqueous solu-
tion is adjusted to pH 9.4 with sodium hydroxide
Number of patients scheduled for 803
therapy
and contains the following:
Placement of catheter successfully 761 (94.8 %)
Mean stone number and range 7.0 (1 - 68) disodium ethylenediaminetetraacetate 1.0 %
Mean stone size (cm) and range 1.6 (0.3-4.5) cholic acid 0.5 %
Patients with solitary stones 197/761 (25.9 %) ursodeoxycholic acid 0.5 %
Patients with multiple stones 564/761 (74.1 %) carnosine 0.5 %
Stone dissolution (> 90 % of stone 724/803 (95.1 %) arginine 1.9 %
burden)
724/724 (90.2 %)
Residual sludge in the gallbladder after 315/724 (43.5 %)
The ethylenediaminetetraacetate solution
catheter removal acts by chelating calcium from calcium biliru-
Bile leak after catheter removal 39/761 (5.1 %) binate to produce sodium bilirubinate which
Patients with minor complications 129/803 (16.1 %)
Method related lethality 0/803 (0 %)
is water soluble [55]. In combination with
30-day lethality 3/803 (0.4 %) PTL – MTBE therapy (described in Section 2.3),
it can also be used for the direct treatment of pig-
ment stones in the gallbladder.

2.6. Critical Assessment of Chemical
Stone Dissolution
Any new method for treatment of gallstones
must be compared with surgery (cholecys-
tectomy) which has been practiced since
1882. Cholecystectomy has an age-dependent
lethality of 0.1 – 4 % (mean 0.4 %) and is a well-
established, low-risk method. However, despite
modern presurgery diagnostics, 25 – 40 % of pa-
tients who have undergone surgery suffer from
the postcholecystectomy syndrome (i.e., from
the same complaints as before surgery) [56],
[57]; in ca. 10 – 15 % of all patients, recurrent
stones develop in the bile ducts [50].
The advantages of oral stone dissolution with
cheno- or ursodeoxycholic acid are the easy ad-
ministration of the preparation and the absence
of fatalities. A disadvantage is the high rate of
stone recurrence (ca. 40 %). The cost is identical
to that of surgical therapy.
A final assessment of PTL – MTBE treatment
is still premature. Extracorporeal shock-wave
lithotripsy with subsequent oral litholysis may
be useful in the treatment of stones with diame-
ters >1.5 cm.
A logical therapeutic concept for treating
gallstones is as follows:
1) Silent gallbladder stones should not be
treated but should be monitored.
2) Cholesterol stones in a functioning gallblad-
der, which have a diameter of 1.5 – 2.0 cm
and produce mild symptoms, are suitable for
oral litholysis.
3) Cholesterol stones with a diameter of
1.5 – 2.0 cm in a functioning gallbladder are
suitable for the combination for ESWL ther-
apy and oral dissolution with bile salt.
4) Cholesterol stones in a functioning gall-
bladder, which measure up to 3 – 4 cm or
fill the gallbladder to more than 50 % and
produce marked symptoms, are suitable for
PTL – MTBE therapy.
5) Surgery is indicated in patients with frequent
colics and all complications (e.g., cholecys-
titis, shrunken gallbladder, empyema, ob-
structed cystic duct, calcified stones, and pig-
ment stones).
6) Since laparoscopic cholecystectomy has
been introduced in 1985, oral litholysis,
ESWL therapy and contact litholysis with
Gallbladder and Liver Therapy 9
MTBE are less important in the treatment of
gallstone disease. The advantages of laparo-
scopic operations are: a lower lethality rate, a
shorter hospital stay, rapid reconvalescence.
The disadvantages are: a higher morbidity
rate and higher costs.
3. Liver Therapeutics
3.1. Introduction
Drug therapy for liver disease is unsatisfactory
from many points of view. Because the liver
occupies a key position in metabolism, it has
an enormous amount of reserve energy that is
used to only a small extent under normal circum-
stances. It receives a more than adequate supply
of the building blocks required for its varied,
rapid metabolic reactions via the portal vein and
the hepatic artery. Like all other parenchyma-
tous organs, the liver requires stimulation of its
functions to maintain its normal structure [58].
Partial, temporary, or permanent collapse of
liver function caused by serious injury to the or-
gan cannot be overcome by drug administration.
Similarly, irreversible structural changes cannot
be reversed by pharmacotherapy [59].
Prophylactic therapy can be used to prevent
liver damage. Additional, medicinal protection
is possible to only a limited extent and is nor-
mally unnecessary because of the liver’s enor-
mous reserve energy supply and regenerative ca-
pacity. This might appear improbable in view of
the range of preparations available on the Eu-
ropean market for the “protection” of the liver.
However, critical analysis of these preparations
shows that they are:
1) experimental products used without any sci-
entific basis,
2) substances uncritically recommended for
use in humans on the basis of animal exper-
iments, or
3) products chosen on the basis of speculation
and inadequate knowledge of intermediary
metabolism.
Liver disease is caused by many different
pathogenic agents; consequently, no single drug
can be effective against all types of disease.
The task of the clinician is to find out which
 10 Gallbladder and Liver Therapy
therapeutic measures can be employed to re-
store liver functions that have failed partially or
totally. Potentially successful therapeutic sub-
stances should possess the following pharmaco-
logical properties:
1) Stimulation of the lowered cell metabolism
2) Stimulation of the reticuloendothelial sys-
tem, particularly in the hepatic region,
thereby causing an increase in the phagocytic
capacity of the reticuloendothelial Kupffer
cells
3) Maintenance or recovery of the intra- and ex-
tracellular structure of the membrane and its
functions
4) A positive regenerative effect
5) An anti-inflammatory effect
6) Antitoxic properties
7) Good absorption from the digestive tract
8) Preferential excretion in the enterohepatic
circulation
9) Lack of properties that are toxic or impose a
stress on liver cells
10) Enhancement of detoxification by effective
entrapment of radicals
11) Absence of side effects
The vitamins, amino acid cocktails, and other
preparations available for protection of the liver
should be considered obsolete. Only a few sub-
stances are important for the treatment of liver
disease; these include the corticosteroids, im-
munosuppressive agents, and silymarin [60],
[61].
Almost all the therapeutic measures dis-
cussed below had their origins in the United
States, where they have long since been for-
gotten. However, they seem to have an unde-
served ability to survive in continental Europe
[59], [62], [63].
The classical experiments of Opie and Al-
ford proved that animals fed a carbohydraterich
diet could withstand chloroform-induced narco-
sis better than those receiving a low-carbohy-
drate diet. Liver glycogen has since been con-
sidered to be one of the factors responsible for
the protection of liver cells. Subsequent animal
experiments demonstrated that chloroform sen-
sitivity was associated with protein, rather than
sugar, metabolism; thus proteins became of in-
terest. In rats, deficiency or lack of the lipid-
mobilizing (lipotropic) substances choline and
methionine caused fatty liver and led to cirrhosis,
whereas a diet lacking cystine (or cysteine), me-
thionine, and vitamin E resulted in liver necrosis
[60], [64], [65]. These animal experiments, how-
ever, were carried out under extreme conditions
that are unlikely to occur in humans. Choline,
cysteine, and methionine were used either singly
or in combination in most of the so-called prepa-
rations for “protection” of the liver. As expected,
they never produced convincing results [66–68].
Different vitamins, particularly those belong-
ing to the B group, form the “hard core” of liver
protection therapy. Of these, vitamin B12 is the
most important. Although the ineffectiveness of
vitamin B12 therapy in acute hepatitis, chronic
hepatitis, and liver cirrhosis has been proved bio-
chemically and clinically [60], it is still remark-
ably popular. The effectiveness of various vita-
min combination drugs has not yet been proved
by controlled chemical trials.
3.2. Therapeutic Agents
Liver diseases are heterogeneous and differ in
their etiology. This fact must be taken into con-
sideration in their treatment. After careful diag-
nosis, a suitable substance must be selected to
achieve a therapeutic effect.
3.2.1. Inhibitors of Viral Nucleic Acid
Synthesis
Acyclovir [59277-89-3], 9-(2-hydroxyeth-
oxymethyl)guanine, is a nucleoside with very
low toxicity and strong virostatic properties
(→ Chemotherapeutics).
In herpes virus infections, acyclovir must first
be activated to acyclovir monophosphate by the
viral thymidine kinase and then converted to
acyclovir triphospate by cellular phosphotrans-
ferases. Acyclovir triphosphate inhibits viral
DNA polymerases by competitively displacing
deoxyguanosine. Although the hepatitis B virus
(HBV) does not possess any endogenous thymi-
dine kinase, a transient decrease in HBV-specific

DNA polymerase has been described in some
cases [69]. Intravenous administration was ac-
companied by some serious side effects, while
very low concentrations in blood plasma could
be detected after oral administration of the drug.
Proacyclovir ( 6-desoxyacyclovir) BW515 is ab-
sorbed very well from the intestine. Results in-
dicate that acyclovir and proacyclovir could be-
come valuable adjuvant drugs in a virostatic
combination therapy for chronic hepatitis B [70–
73] .
Trade Name.Zovirax (Wellcome, Burgwedel)
Intercalary Substances. Some substances
that can inhibit DNA polymerase in vitro
(quinacrine, chloroquine, chlorpromazine, and
primaquine) have also been tested in clinical
studies on patients with chronic hepatitis B.
Therapeutic efficiency has not yet been proved
[72], [74], [75].
Interferon. Interferon comprises a set of bio-
logical proteins with antiviral and immunomod-
ulatory activity (→ Interferons). Interferons can
alter the course of viral infection by inhibiting
intracellular virus replication and by modifying
the immune responses to viral antigens in body
fluids and on cellular surfaces [76–78]. The α-
and β-interferons are induced by viral replica-
tive events in all types of cells and are thus prob-
ably important during the early phases of an in-
fection [58]. γ-Interferon is produced as a result
of the formation of antigen-sensitized T cells and
probably exerts its effect during later stages or
during chronic infection [77], [79], [80].
Phosphonoformic Acid [4428-95-9].
Sodium phosphonoformate [63585-09-1 ]
is a pyrophosphate analogue that selec-
tively inhibits viral nucleic acid synthesis
(→ Chemotherapeutics). The formation of
triphosphate nucleotides by polymerases, which
is essential for the synthesis of RNA and DNA,
is prevented by this substance [78]. The HBV
DNA polymerase is also inhibited by phospho-
noformic acid in vitro and in experiments on
chimpanzees. However, the substance does not
appear to be suitable in the treatment of humans,
because the phosphate moiety may accumulate
in the bones and delayed toxic effects cannot
be ruled out. Moreover, it must be administered
intravenously at relatively short intervals, which
Gallbladder and Liver Therapy 11
makes long-term treatment difficult [72], [74],
[77].
Ribavirin [36791-04-5], 1-β-d-ribofurano-
syl-1H-1,2,4-triazole-3-carboxamide, is a nu-
cleoside analogue that acts against a broad
spectrum of RNA and DNA viruses in vitro
by inhibiting the biosynthesis of guanosine
monophosphate. It accumulates in the liver
but does not appear to affect the reproduction
of HBV. Therapeutic tests show that the sub-
stance does not favorably influence the course
of chronic hepatitis B [80], [81].
Vidarabine [24356-66-9], 9-β- d-arabino-
furanosyl-adenine (ara-A) and its monophos-
phate ( ara-AMP) [29984-33-6] are purine
nucleosides with strong virostatic properties
(→ Chemotherapeutics). They selectively in-
hibit the activity of viral DNA polymerase and
thereby prevent synthesis of the complementary
minus-strand DNA from the viral pregenome
[82], [83].
The decrease in DNA polymerase activity
specific to hepatitis B virus is faster and greater
after treatment with ara-A or ara-AMP than
with interferon. However, when treatment is
discontinued, DNA polymerase activity usually
reaches the initial values observed before treat-
ment. Continued inhibition of HBV replication
after discontinuation of therapy occurs about as
often as after treatment with interferon [84]. In
comparison with the monophosphate ester ara-
AMP, ara-A has the disadvantage of requiring
large infusion volumes in clinical therapy. Gen-
erally, therefore, the more water-soluble deriva-
tive ara-AMP is used. The monophosphate ara-
AMP can also be administered intramuscularly
and is suitable for treatment of outpatients. How-
ever, daily dosages of 5 – 10 mg per kilogram of
body weight for a period of 28 days are only
12 Gallbladder and Liver Therapy
slightly effective. Longer treatment periods or
higher doses lead to serious, extremely painful
and long-lasting polyneuropathies that disap-
pear very slowly after discontinuation of treat-
ment. This neuromuscular pain syndrome be-
gins mainly in the lower extremities in the form
of a “burning feet syndrome.” Other side effects
include tiredness, listlessness, loss of appetite
(occasionally with mild nausea), and slight de-
pletion of bone marrow which is reversible after
discontinuation of the drug [73], [82].
Trade Name. Vidarabin (Dr. Thilo, Sauerlach)
3.2.2. Bile Salts used for Primary Biliary
Liver Disease
Ursodeoxycholic acid is a naturally occur-
ring bile salt in humans. It is rapidly absorbed
in the small intestine and excreted with the bile.
Ursodeoxycholic acid is the drug of choise for
the treatment of primary biliary cirrhosis and
primary sclerosis cholanyitis. The daily dose
amounts to 10 – 15 mg/kg. It has no side effects
even after a treatment period of up to 20 years.
In primary biliary cirrhosis, it improves the
laboratory data significantly by 50 – 80 % and
the symptoms in 30 – 40 % of the patients. Ur-
sodeoxycholic acid prevents or delays the de-
velopment of oesophageal varices and prolongs
life expectancy. Better results are obtained when
ursodeoxycholic acid is combined with the glu-
cocorticoid budesonide.
3.2.3. Natural Substances
Cyanidanol [154-23-4], Catergen, (+)-
catechin, (+) 3-cyanidanol, (2R,3S)-3,3 ,4 ,5,7-
pentahydroxyflavan, was isolated in 1830 from a
series of plants of African, American and Indian
origin (Uncaria gambir). Unequivocal elucida-
tion of its stereochemical structure was carried
out in the late 1950s [85].
Cyanidanol is absorbed rapidly from the gas-
trointestinal tract. Its concentration in blood
reaches a maximum after 1 – 2 h. Excretion takes
place mainly as the glucuronide and sulfate con-
jugates in the urine [86–88].
Unchanged cyanidanol is present in only
small amounts in the liver because almost all
of it is metabolized rapidly during its first pas-
sage through the organ. Eleven metabolites have
been isolated [89–92].
Investigations with radioactively labeled
cyanidanol have shown that about 27 % of the
administered dosage is excreted in the urine after
3 h and between 70 and 88 % after 27 h. This cat-
echol lacks liver specificity because of its rapid
urinary elimination. Furthermore, the substance
is inactivated where it is supposed to act, i.e., in
the liver. Because of its serious, sometimes fatal
side effects, this compound was withdrawn from
the market in 1987 [92–94].
Silymarin is obtained from the milk thistle –
Silybum marianum (L.) Gaertn. or Carduus mar-
ianus (L.) – a medicinal plant known since an-
cient times. For structural elucidation and total
synthesis of the constituents of silymarin, see
[94], [95]. Silymarin is a general term used to
describe three substances derived from the milk
thistle fruit: silybin [22888-70-6], silydianin
[29782-68-1], and silychristin [33889-69-9].
For structural elucidation of these compounds,
see [96], [97].

The effects of silymarin and its main con-
stituent, silybin, were investigated on different
models of liver damage in acute, subchronic, and
chronic experiments on animals. Treatment was
either prophylactic or curative [98–100].
Silymarin is active against a large number of
hepatotoxic substances. It exerts a positive influ-
ence on several basic cellular functions, namely,
membrane integrity, of ribosomal RNA and thus
of proteins, and the regenerative capacity of the
liver [101], [102]. Most of these functions are
influenced only in the damaged liver and not in
a healthy liver [103–105].
Preparations like silymarin have a protective
and stabilizing effect on the liver cell mem-
brane due to their radical scavenger function and
the resultant preventation of lipid peroxidation.
Furthermore, silymarin has an immunomodula-
tory effect (normalization of the reduced lym-
phoblastic transformation activity of cirrhotic
patients). Both the immunomodulatory and an-
tioxidant activities of silymarin ( Legalon) play
an important role in the mode of action of this
hepatoprotective preparation [64], [65], [101],
[106–108].
Pharmacokinetics. About 90 % of silymarin
is excreted in the bile; renal elimination accounts
for ca. 10 %. The compound is conjugated in
the form of glucuronides, sulfates, and sulfaglu-
curonides in the liver. These conjugates are then
cleaved by the intestinal flora, and the active in-
gredient is reabsorbed. About 40 % of the ab-
sorbed substance enters this cycle, i.e., the en-
terohepatic circulation. Silymarin does not in-
duce enzyme synthesis; interaction with other
drugs has not been observed [64], [65], [109],
[110].
Use in Alcohol-Induced Liver Disease. The
therapeutic action of silymarin in diseases of the
liver caused by alcohol has been well established
[111–113].
The efficacy of Legalon was investigated in
a double-blind study of alcohol-induced liver
damage. The serum (GPT) glutamic – pyruvic
transaminase and glutamic – oxalacetic
transaminase (GOT) values, bromsulphalein
(BSP) retention, and histological changes nor-
malized more rapidly and more frequently in
patients receiving the drug than in the control
group [114].
The efficacy of silymarin was shown in pa-
tients with alcohol-induced liver disease in a ran-
Gallbladder and Liver Therapy 13
domized double-blind study. The serological pa-
rameters bilirubin, GOT, GPT, glutamate dehy-
drogenase (GLDH), γ-glutamyltransferase (γ-
GT) and alkaline phosphatase were chosen for
monitoring. Other serological and sonographic
findings were used as general clinical controls.
The results, particularly changes in γ-GT, GPT,
GOT showed that Legalon produced significant
improvement [113], [115].
Use in Occupational Liver Disease. Sily-
marin treatment of patients suffering from oc-
cupational liver disease led to considerable
improvement of parameters that showed ele-
vated pathological values: alkaline phosphatase,
bilirubin, GOT, GPT, γ-GT, and cholinesterase
[116–118].
The action of Legalon on liver function after
cholecystectomy was investigated in a double-
blind study. The values for GPT and γ-GT
showed a statistically significant difference in
favor of Legalon [61], [63].
The above results confirm other inves-
tigations on the postoperative behavior of
cholinesterase and various hepatic enzymes in
the presence of Legalon [112], [119].
Silymarin produced an antihepatotoxic ef-
fect, as well as a decrease in lipoprotein and
triglyceride concentrations, in patients with liver
damage resulting from industrial toxicity caused
by silicon dioxide, lead, trinitrotoluene, and tri-
chloroethylene. In workers from the chemical
industry who were exposed continuously to xy-
lene and/or toluene, Legalon had a signifcant
protective effect on the liver [59], [60], [64].
Use in Liver Cirrhosis. In a randomized
double-blind study, 170 patients with cirrhosis
of the liver were treated with silymarin: 87 pa-
tients received 140 mg Legalon three times daily,
83 patients received a placebo. The average ob-
servation time was 41 months for the placebo
group and 50 months for the group receiving
Legalon. The survival rate was 76 ± 6 % (stan-
dard error) in patients treated with silymarin and
53 ± 8 % in the placebo group. Analysis of the
subgroups indicated that treatment was effective
in alcoholic cirrhosis as well as in cases classi-
fied as a cholangic biliary cirrhosis (an ailment
affecting children up to 12 years of age). These
results show that mortality in cirrhosis patients
is lowered by treatment with silymarin [120].
In a multicenter study of Amanita phalloides
intoxication in the Federal Republic of Germany,
14 Gallbladder and Liver Therapy
Switzerland, Austria, and France, a survival rate
of 91.6 % was observed in 220 patients treated
with silybinin. Silybinin infusions in combina-
tion with conventional treatment represent an ef-
fective therapeutic supplement in patients with
Amanita phalloides intoxication [106], [121–
123].
Trade Names. Legalon 70, Legalon 140, Lega-
lon Sil Ampullen, Legalon Liguidum (Dr.
Madaus, Köln).
3.2.4. Miscellaneous Substances
“Essential” Phospholipids. Lecithin has
been used in therapy as a hepatotropic substance
ever since the liver was shown to incorporate
choline into lecithin. “Essential” phospholipids
(EPL) are derived from a special fraction of
lecithin and isolated by chromatographic meth-
ods from a crude mixture of phospholipids ob-
tained from soybean. They consist of naturally
occurring phosphatidylcholine with an espe-
cially high content of polyunsaturated, essential
fatty acids, particularly linoleic acid [124–128].
More than 50 % of EPL consists of phospha-
tidylcholine in which the substituents R1 and R2
are derived from linoleic acid:
CH3 (CH2 )4 CH=CHCH2 CH = CH(CH2 )7 COOH
The essential phospholipids differ from the
phospholipids present in the body in that R1
is derived from a polyunsaturated fatty acid
(mainly linoleic acid) and not a saturated one
[129], [130].
Production. Commercially available crude
phosphatides of plant origin are dissolved in
ethyl acetate, a lower dichlorohydrocarbon, or
a mixture of the two; up to 6 vol % of alcohol
may also be present. Stirring with a quantity of
aluminum oxide corresponding to at least five
times the crude mass of phosphatides and subse-
quent elution of the adsorbent with alcohol give
a product that contains >90 % phosphatidylcho-
line. Pure phosphatidylcholine can be obtained
by using propylene dichloride for desorption of
the aluminum oxide, instead of alcohol. After
evaporation of the solvent in an inert atmosphere
under reduced pressure, phosphatidylcholine is
obtained in yields of up to 88 % as an almost
colorless, pasty mass.
Mode of Action. Phospholipids are con-
stituents of biological membranes and, there-
fore, play an important role in membrane-
dependent metabolic processes. On the one
hand, the properties of therapeutically employed
phospholipids containing polyunsaturated fatty
acids should correspond to those native to the
body. However, the cis double bonds in the
polyunsaturated fatty acids prevent parallel
alignment of the hydrocarbon chains of the
membrane phospholipids. This should lead to a
loosening of the tightly packed, micellar phos-
pholipids and thus to a higher transmembrane
exchange rate [129–131].
Therapeutic effects. Lipemia caused by eth-
anol is antagonized by EPL in acute as well
as chronic animal experiments. Serum alkaline
phosphatase and plasma protein fractions of the
plasma tend to return to normal values. Cirrhosis
caused by chronic administration of small doses
of carbon tetrachloride is largely prevented by
the simultaneous administration of EPL. How-
ever, these are less effective in treating poisoning
due to galactosamine, carbon disulfide, and allyl
isothiocyanate [132], [133].
In rats, orally administered EPL were ab-
sorbed completely within 24 h and reached the
liver almost exclusively via the lymphatic sys-
tem [134].
The liver absorbs between 10 and 15 % of the
administered EPL. Excretion occurs slowly via
urine and bile.
Acute viral hepatitis is considered to be
amenable to EPL therapy. Administration of
EPL shortens the duration of hepatitis A and B.
Chronic hepatitis, chronic-aggressive hepatitis,
and liver cirrhosis show clear signs of improve-
ment following treatment with EPL [135–137].
Based on the clinical picture and laboratory
results obtained after EPL therapy, this sub-
stance appears to increase the biochemical ef-
ficiency of residual parenchyma tissues. Iatro-
genic injuries to the liver, caused by treatment of
tuberculosis with isoniazid and rifampicin, can
also be alleviated. Treatment with EPL signifi-
cantly reduces fatty degeneration of liver cells

and alleviates cell membrane injury occurring
during the protein-deficiency disease kwash-
iorkor [138], [139].
The effectiveness of EPL has been proved
pharmacologically, and they are also well tol-
erated clinically. Thus, EPL may be regarded as
a liver curative that intervenes in the form of a
“substitution therapy” in hepatocyte anabolism
and liver disease in which an activation of an-
abolic processes appears desirable [140–142].
Trade Name. Essentiale (Nattermann, Köln).
Orotic acid [65-86-1], 1,3,5-trihydro-2,6-
dioxopyrimidine-4-carboxylic acid, uracil-
6-carboxylic acid, whey acid, C5 H4 N2 O4 ,
M r 156.10, mp 345 – 346 ◦ C [143–145].
Production. The oldest known method for
synthesizing orotic acid is the condensation of
urea with diethyl oxalacetate and subsequent al-
kaline hydrolysis of the reaction product. Free
orotic acid is obtained from the alkali salt by
treatment with mineral acid [124–126].
A newer synthesis starts by condens-
ing chloroacetoacetyl chlorine, obtained from
diketene and chlorine, with urea to give 6-chlo-
romethyluracil. Oxidation of the latter with hy-
drogen peroxide in an alkaline medium yields
orotic acid [134], [146].
In another method, hydantoin or hydantoni-
trile is treated with glycolic acid in an alka-
line medium to give carboxymethylene hydan-
toin, which rearranges to form orotic acid [145],
[147].
Orotic acid is also produced in fermentation
by using microorganisms such as Corynebac-
terium, Brevibacterium, Arthrobacter, and Can-
dida [148], [149].
Mode of Action. In the liver, orotic acid is the
precursor of the pyridine nucleotides of nucleic
acid (→ Nucleic Acids). As a parenchymatous,
glandular organ, the liver is rich in cell nuclei,
where the nucleic acids are localized. Cow’s
milk also contains a relatively high concentra-
tion of orotic acid (6 – 10 mg/L).
Orotic acid is synthesized in the liver from
aspartic acid and carbamyl phosphate in two
Gallbladder and Liver Therapy 15
steps. It is the precursor of the simplest pyrim-
idine nucleotide, uridine monophosphate, and
of deoxythymidine monophosphate. The corre-
sponding triphosphates are building blocks for
ribonucleic and deoxyribonucleic acids (RNA
and DNA, respectively; → Nucleic Acids) [127–
131].
Uridine triphosphate is a coenzyme for the
transfer of uronic acids. Uridine diphosphate
glucuronic acid, and thus orotic acid, play a vi-
tal role as glucuronate donor in detoxification
and elimination of substances such as steroids,
drugs, and bilirubin. Although orotic acid is an
essential compound for many microorganisms,
it does not have any vitamin-like character in
mammals [129], [130], [132], [133].
Trade Name. Hepatofalk (Dr. Falk GmbH,
Freiburg).
Thioctic acid [62-46-4], 5-(1,2-dithiolan-3-
yl)valeric acid, α-lipoic acid, C8 H14 O2 S2 ,
M r 208.31, mp 47.5 – 48 ◦ C, forms yellowish
flakes and is sparingly soluble in water, but solu-
ble in methanol, ethanol, diethyl ether, and chlo-
rofom.
Thioctic acid is widespread in the plant and
animal kingdom. It can be prepared by reacting
6,8-dichlorooctanoic acid with sodium disulfide
(Na2 S2 ) (for this and other methods of synthesis,
see [150–152]).
Production. Industrial synthesis of thioctic
acid is performed in three stages. Monomethyl
or monoethyl adipate is converted into the corre-
sponding acid chloride by reaction with thionyl
chloride. Treatment with ethylene in the pres-
ence of anhydrous aluminum chloride yields 8-
chloro-6-ketooctanoate. In the second stage, this
ester is reduced to 8-chloro-6-hydroxyoctanoate
by using thionyl chloride in pyridine. In the
third stage, the chlorine atoms are replaced by
sulfur atoms by treatment with sodium disul-
fide. Hydrolysis of the resulting dithionooctyl
ester formed with alcoholic potassium hydrox-
ide gives thioctic acid [153], [154].
Mode of Action and Pharmacology. The
concentration of thioctic acid is highest in the
liver. Its main biochemical role is as a coen-
16 Gallbladder and Liver Therapy
zyme in the oxidative decarboxylation of α-
keto acids. It is a constituent of acid reductase
transacetylase, liponamide oxidoreductase, and
the α-ketoglutarate dehydrogenase complex.
Detoxifying properties can be expected from
the five-membered disulfide ring, particularly
that function as enzyme inhibitors [152], [155–
157].
Thioctic acid is a growth factor for only cer-
tain protozoa and bacteria. However, in verte-
brates it is formed by biosynthesis and thus a
deficiency does not occur in humans. Neverthe-
less, it has been recommended in the treatment
of hepatic coma, chronic hepatitis, and cirrhosis.
Expectedly, no reproducible clinical success has
been achieved. The antitoxic properties of thioc-
tic acid have been utilized with partial success,
for example, in treatment of poisoning caused by
the deadly amanita (death cap) mushroom [158].
In humans, thioctic acid is excreted mainly
in the urine within 24 h of a single oral or par-
enteral dose. In rats, the mucous membrane of
the isolated duodenum rapidly absorbs thioctic
acid within 45 min [159–162].
Trade Name. Thioctacid (Chemiewerk Hom-
burg, Frankfurt)
3.2.5. Antifibrinogenic Drugs
Antifibrinogenic drugs inhibit the formation of
fibrin.
Colchicine [64-86-8], isolated from the
meadow saffron ( Colchicum autumnale ; for
structure and production, see → Alkaloids,
Chap. 9.23.), was the first natural substance rec-
ognized for its antimitotic effect. This water-
soluble alkaloid is quickly absorbed from the
intestine and binds strongly to plasma proteins
and cell proteins ; it is deacetylated in the liver.
Colchicine accumulates in the body due to its
slow breakdown, entrance into the enterohepatic
circulation, and high protein binding. Colchicine
inhibits microtubular protein assembly in fi-
broblasts, and thereby collagen formation. Toxic
dosage produces acute renal damage and ascend-
ing paralysis, as well as chronic agranulocytosis,
hair loss, and myopathy [163–165].
Over 4 years, 23 patients with liver cirrho-
sis received colchicine (1 mg/day, 5 days/week)
and 20 a placebo [166]. Mortality decreased
from 40 % with placebo to 17 % in the treat-
ment group, but this decrease was not sta-
tistically significant. Ascites, encephalopathy,
and splenomegaly improved significantly in the
group receiving colchicine. Although the results
of this study are encouraging, confirmation in a
larger population sample is needed [166–171].
d-Penicillamine [52-67-5], C5 H11 NO2 S,
M r 149.21, mp 198.5 ◦ C, is a dimethyl deriva-
tive of the amino acid cysteine, which contains a
sulfhydryl group (for production, see → Amino
Acids).
The biochemical and pharmacological effects
of d-Penicillamine can be explained by three im-
portant reactions:
1) Chelation of heavy metals
2) Exchange reaction with disulfides
3) Reaction with aldehydes
Treatment of chronic – aggressive hepatitis with
d-Penicillamine is based on the following mech-
anism of action [172], [173]:
d-Penicillamine reacts with the aldehyde
groups of the collagen precursor tropocolla-
gen to form thiazolidines. This prevents cross-
linking of tropocollagen and thus the synthesis
of insoluble collagen. Inhibition of collagen syn-
thesis has been shown in animal experiments
where d-penicillamine disturbs wound healing,
decreases the tensile strength of the skin, and
increases dilatory capacity of the lungs due to
lowered elastic resistance [173], [174].
The importance of these effects is evi-
dent in diseases in which the major patholog-
ical symptom is an excessive proliferation of
mesenchyma. The inhibitory influence of d-
penicillamine on the inflammatory mesenchy-
mal reaction (i.e., on cell proliferation) can be
seen clearly in liver punctates [175–177].
d-Penicillamine does not dissolve or “soften”
cirrhotic cicatrizations (scars). However if treat-
ment is started at an early stage, the histolog-
ically active process may be retarded to allow
healing of the residual fibrosis. This possibil-
ity assumes particular significance when other

methods of treatment are unsuccessful [178–
180].
Trade Name. Metalcaptase (Knoll, Lud-
wigshafen; Heyl, Berlin)
Insulin and Glucagon. In animal experi-
ments, the presence of hepatotrophic factors in
portal blood has repeatedly been documented
[58]. Insulin and glucagon were shown to be
particularly potent stimuli of hepatocellular re-
generation [181]. Administration of these hor-
mones ameliorated fulminant murine hepatitis
[182]. Stimulation of regeneration by infusion
of these hormones may be a useful approach
for treatment of severe alcoholic hepatitis in hu-
mans.
A randomized, double-blind controlled trial
of insulin and glucagon infusion has been con-
ducted on patients with alcoholic hepatitis [183].
Twenty five patients received 24 units of insulin
and 2.4 mg glucagon over 12 h daily for 3 weeks;
another 25 patients received dextrose solution as
placebo. Mortality in the treatment and placebo
group was not significantly different. However,
in a subgroup of 34 patients with prolonged
prothrombin times, fewer deaths were observed
in the treatment group. In addition, total serum
bilirubin and prothrombin time improved more
rapidly in the insulin- and glucagon-infused
group. Complications included hypoglycemia,
superficial thrombophlebitis at the site of infu-
sion, and generalized macular skin eruptions.
This type of therapy, although still experimental,
seems to be a promising approach for the seri-
ously ill patients, in whom the rate of hepatocel-
lular regeneration might be critical for survival
[184].
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Gallium and Gallium Compounds
Jörg Friedrich Greber, INGAL International Gallium GmbH, Schwandorf, Federal Republic of Germany
1. Introduction . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . .
3. Chemical Properties . . . . . . . . .
4. Occurrence and Raw Materials . .
5. Production . . . . . . . . . . . . . . .
1. Introduction
Gallium [7440-55-3] is an element of group 13.
Its existence was predicted by Mendeleev,
and it was discoveredby Lecoq de Bois-
baudran in 1875. The metal was mainly
of academic interest until 1970, when it
was found that compounds of gallium with
group 15 elements have semiconducting proper-
ties (→ Semiconductors), and so began the ex-
tensive industrial use of the element. Gallium
compounds are of particular value in optoelec-
tronics, especially for light-emitting diodes.
2. Physical Properties
Gallium is a silvery-white metal, mp 29.78 ◦ C,
bp 2403 ◦ C. The naturally occurring element
contains two stable isotopes: 69 Ga (60.4 %)
and 71 Ga (39.6 %). The density of the liquid
is 6.095 g/cm3 at 29.8 ◦ C, and the density of the
solid is 5.904 g/cm3 at 24.6 ◦ C. There is a vol-
ume expansion of 3.2 % on solidification.
Gallium forms orthorhombic crystals
with the lattice constants a = 0.4523 nm, b =
0.45198 nm, and c = 0.76602 nm, and the
physical properties are consequently strongly
anisotropic. The thermal expansion coeffi-
cients are 1.65×10−5 K−1 along the a axis,
1.13×10−5 K−1 along b, and 3.1×10−5 K−1
along c. The electrical properties are equally

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a12 163
Gallium and Gallium Compounds 1
. . . 1 6. Storage and Transportation . . . . . . . 5
. . . 1 7. Uses . . . . . . . . . . . . . . . . . . . . . . . 5
. . . 1 8. Economic Aspects . . . . . . . . . . . . . 5
. . . 2 9. Toxicology and Industrial Medicine . . 6
. . . 2 10. References . . . . . . . . . . . . . . . . . . 6
anisotropic, but it is not possible to quote reli-
able figures owing to the great influence of purity
and temperature on the electrical conductivity.
3. Chemical Properties [1–4]
Metallic gallium dissolves only slowly in dilute
mineral acids, but rapidly in aqua regia and con-
centrated aqueous sodium hydroxide. It also dis-
solves slowly in solutions of hydrogen halides in
ether.
In its compounds, the valency of gallium
is usually 3. The monovalent state is unstable,
although the monovalent gallium compounds
Ga2 O and GaCl can be isolated. An oxidation
state of +1 has not yet been detected in aqueous
solution, but some reactions of gallium indicate
that it exists.
The oxygen compounds of gallium resemble
those of aluminum in that there are high and low
temperature forms of Ga2 O3 and two hydrox-
ides, Ga(OH)3 and GaO · OH. Gallium halides
have covalent character and therefore have good
solubility in many nonpolar solvents in which
they exist in dimeric form.
With elements of group 15, gallium forms bi-
nary compounds, of which GaP [12063-98-8]
and GaAs [1303-00-7] areof great industrial im-
portance. They may be prepared by direct com-
binationof the elements at high temperature.
In aqueous solution, gallium forms octahe-
drally coordinated aquo ions [Ga(H2 O)6 ]3+ .
2 Gallium and Gallium Compounds
There are many salts of oxoacids, such as the sul-
fate, nitrate, and perchlorate, and also hydrated
halides.
In aqueous solution, the hexaaquo complex
has an acid reaction owing to hydrolysis. Gal-
lium salts of weak acids cannot exist in the
presence of water for the same reason. Of the
numerous anionic and cationic complexes, the
most industrially important are the halide com-
plexes, the [GaX4 ]− ions, whose oxonium salts
have good solubility in several organic solvents.
This property is utilized in the extraction and
purification of the metal. Other gallium com-
plexes of industrial importance are the octa-
hedrally coordinated chelates with β-diketones
and 8-hydroxyquinolines, these also being sol-
uble in organic solvents. Alcoholates and or-
ganic derivatives may be prepared similarly to
the analogous aluminum compounds.
Gallium forms a series of alloys with other
metals, sometimes even at low temperatures.
Some of these, containing up to 3 % gallium,
are useful in dentistry.
4. Occurrence and Raw Materials
With its natural abundance of 16 ppm, gallium
is one of the rarer elements in the earth’s crust.
Gallium-containing minerals, the best known of
which is a variety of germanite, do not have
economic significance. Of the known locations,
only the Apex mine in Utah has been commer-
cially mined.
The greatest part of the world production of
gallium is as a byproduct of the production of
aluminum oxide. The gallium concentration in
bauxite ranges between 0.003 and 0.008 %, de-
pending on the location. The high contents oc-
cur in tropical bauxites such as Surinam bauxite,
which contains 0.008 % Ga, the highest average
content known. The world supply of recover-
able gallium in bauxite is estimated at 1.6×106 t
based on bauxite reserves and their gallium con-
tents [5].
Because of the low concentration of gallium
in bauxite, it is not economic to mine bauxite to
extract gallium. The amount of gallium available
from bauxite is then determined by the amount
of aluminum oxide that is produced. For the year
1986, complete utilization of the gallium from
aluminum oxide production would have corre-
sponded to a theoretical production of ca. 2000 t
of gallium. The gallium contained in zinc ore
(sphalerite) has lost economic importance due
to the changeover to hydrometallurgical meth-
ods of zinc extraction. The reserves of gallium
in zinc ores worldwide has been estimated to be
6500 t [5].
The largest reserves of gallium are contained
in phosphate ores and in coal of various kinds.
When phosphorus is produced electrothermally
from phosphate, the gallium is concentrated in
the flue dust and may be recovered from it. Like-
wise, gallium may be obtained from the fly ash
of coal, another material in which gallium is con-
centrated. Neither source is exploited at present
because the gallium concentration is only 0.01 –
0.1 wt %. It is not economic to treat these ma-
terials merely to extract the gallium. The total
gallium reserves in phosphates and coals have
been estimated at several million tonnes. They
thus considerably exceed those in bauxite [5].
5. Production
The most important process for gallium pro-
duction is the extraction of the metal from
the circulating liquors in the Bayer process
for aluminum oxide manufacture (→ Aluminum
Oxide, Chap. 3.). These contain 70 – 150 mg/L
of gallium, depending on the bauxite and on the
concentration of the caustic liquor. The gallium
content of the liquor is also determined by the
dissolution process used. Bauxite which is high
in boehmite (AlO · OH) requires high tempera-
tures for the dissolution process, leading to more
complete release of the gallium and higher con-
centrations in the circulating liquors.
The gallium extraction plant is usually lo-
cated within or very near to the aluminum oxide
works. Part of the liquor stream is diverted for
gallium extraction and then recycled. In some
instances the liquor undergoes a preliminary pu-
rification process to remove certain heavy met-
als.
Three types of process are used to extract
the gallium from the circulating liquor: (1) frac-
tional precipitation, (2) electrolytic processes,
and (3) extraction with chelating agents.
Fractional Precipitation. The basis of this
process is that when the gallium-containing
sodium aluminate solution is treated with car-
bon dioxide the first product precipitated is pure
 Gallium and Gallium Compounds 3

aluminum hydroxide. This increases the gal- of electrolytic processes. These processes are,
lium content of the liquor. Further treatment then however, in operation in Hungary, Czechoslo-
causes the gallium to separate along with more vakia, the German Democratic Republic, and the
aluminum hydroxide. After this, fractional pre- Federal Republic of Germany. About 15 – 20 t/a
cipitation gives an aluminum hydroxide richer of gallium is produced.
in gallium, and this is followed by one or more Extraction with Chelating Agents. The dis-
further fractional precipitations. The gallium- covery was made in 1974 that hydroxyquino-
enriched aluminum hydroxide is dissolved in lines could be used to extract gallium from
aqueous sodium hydroxide to give a solution sodium aluminate liquors (the Rhône-Poulenc
of sodium aluminate and sodium gallate, from process, Fig. 1) [6], these substances having ear-
which gallium is obtained by electrolysis. lier been developed for the hydrometallurgical
The precipitation process is used only to a extraction of copper. The aluminate liquor is
small extent because of the expense of removing brought into contact with a solution of Kelex 100
the byproduct sodium carbonate unless thermal [29171-27-5] in kerosene.Gallium is thereby ex-
decomposition is used in the aluminum oxide tracted from the liquor along with aluminum
works. Also, on account of the many precipita- and sodium.Most of the elements extracted with
tion stages involved, the process is labor inten- the gallium may be stripped from the extraction
sive and can therefore be used only when energy medium by treatment with dilute acid. The gal-
and labor costs are low. The People’s Republic lium is then extracted with concentrated acid; ei-
of China produces gallium at a rate of 5 t/a by ther hydrochloric or sulfuric acid may be used.
this process. Gallium concentrations of 0.1 – 10 g/L may be
Electrolytic Processes. The electrolytic pro- reached in the acid extract, depending on the
cess depends on the fact that mercury forms method used. The gallium to aluminum concen-
an amalgam with gallium from which the gal- tration ratio in the extract can reach values as
lium may be extracted with a caustic soda so- high as 1, which corresponds to enrichment fac-
lution. The gallium amalgam can be produced tors of up to 1000 in the primary extraction stage.
either directly (Alusuisse process) or indirectly
(VAW/INGAL process).
In the Alusuisse process, the gallium is de-
posited directly onto the mercury cathode, us-
ing the appropriate conditions of temperature,
agitation, and current density, and an amalgam
is formed. In the VAW process, sodium amal-
gam is used to reduce the gallium present in the
Bayer liquor. This gives an amalgam from which
the gallium is removed by treatment with caus-
tic alkali, and the mercury is then used again
to produce sodium amalgam, i.e., the mercury
circulates in a closed system.
Reduction processes have in recent years be-
come less attractive because they require special
conditions to be commercially viable. In partic-
ular, the aluminate solutions must contain over
150 g/L sodium and be very low in vanadium,
tungsten, molybdenum, and iron so that the elec-
trolytic current efficiency reaches economically
acceptable values. However, such highly con-
centrated liquors are not produced in modern Figure 1. Flow diagram showing gallium extraction by the
aluminum oxide plants, and therefore the elec- Rhône-Poulenc and Sumitomo processes
trolytic process can no longer be used in new
installations. The environmental problems asso- Further concentration of the gallium is
ciated with mercury further discourage the use achieved by anion- or cation-exchange treatment
4 Gallium and Gallium Compounds
of the acid extract from the first stage. The metal
can be isolated from this concentrate by direct
electrolysis.
Although the process solutions are recircu-
lated to a large extent, considerable quantities
of waste acid are generated. This waste acid is
contaminated with other extracted metals and
residues from the extraction media. An impor-
tant economic factor in the extraction process
is therefore the possibility to dispose of these
solutions cheaply or to make some use of them.
In the Sumitomo process (Fig. 1) the first
stage is extraction with the ion-exchange resin
Duolite CS-346 (Diamond Shamrock) [7]. This
resin contains amidoxime groups, which form
chelate bonds to gallium. Unlike Kelex 100, this
resin has the drawback that any vanadium ex-
tracted from the aluminate liquors blocks the ion
exchange sites. Vanadium must therefore be re-
moved from the circulating liquor of the alu-
minum oxide plant before gallium extraction.
The rest of the Sumitomo process corresponds
to the Rhône-Poulenc process.
Gallium is produced by extraction processes
in France and Japan.
Purification. The gallium from extraction
processes has a purity of 99 – 99.9 wt %. For
most applications, however, much higher puri-
ties are necessary, reaching 99.999999 % (8N).
Various procedures are used to remove the impu-
rities. Volatile metals, such as mercury and zinc,
are distilled off under vacuum. Further purifica-
tion is effected by washing with aqueous acids
and alkalies. The purest gallium is obtained by
fractional crystallization, zone melting, or sin-
gle crystal growth. Other methods of purifica-
tion include the extraction of gallium chloride
from acid solution and fractional distillation of
liquid gallium compounds.
Environmental Protection. No harmful ef-
fects of gallium or its compounds have been re-
ported. There are therefore no regulations con-
cerning gallium concentrations in exhaust gases
from gallium manufacturing plants. For the ma-
terials used in gallium manufacture, such as mer-
cury or 8-hydroxyquinoline, the relevant legal
requirements must be observed.
Quality. The commercially available materi-
als include a crude grade and various pure grades
of gallium. The crude metal contains 99 – 99.9 %
gallium. The material for semiconductor manu-
facture is used in purities from 99.9999 % (6N)
to 99.999999 % (8N).
Analysis. Gallium is determined in raw ma-
terials and partially enriched intermediate prod-
ucts either by complexometric titration (high
concentrations) or atomic absorption (low con-
centrations).
For the analysis of the purest grades of gal-
lium, it is necessary to have methods of deter-
mining impurities at parts per million to parts per
billion levels. The most important technique is
spark source or glow discharge mass spectrome-
try, which enables heavy metals to be determined
with sufficient accuracy. Lighter elements can be
determined by activation analysis or by special
mass spectrometric techniques.
A general assessment of gallium purity may
be made from its residual resistance ratio. This
is determined from the electrical conductivity of
a gallium single crystal at room temperature and
at liquid helium temperature. This ratio is very
sensitive to the presence of impurities but is non-
specific. Typical values for high purity gallium
are better than 55 000.
6. Storage and Transportation
The low melting point of gallium and the high
purity requirements mean that care must be
taken to prevent gallium from melting or being
contaminated by the packing materials during
storage and transportation. The metal is usually
sold in lumps of 10 g – 2 kg, individually packed
and kept cold in plastic containers.
For short distances, gallium may be carried
by truck or rail, provided that the temperature is
not allowed to exceed 20 ◦ C. For carriage over
long distances, the method chosen is usually air
transport, in which uninterrupted cooling is to
be maintained. Regulations governing packag-
ing for air transport have been laid down by IATA
owing to the ability of gallium to form alloys
with aluminum at normal temperatures, these al-
loys having very low mechanical strength. Gal-
lium must be contained inside seven layers of
packing material and in warm weather the con-
tainer must be cooled. In this way, the danger
of an accident in which the structural metal of
 Gallium and Gallium Compounds 5
Table 1. Gallium production in kilograms of gallium for 1978, 1984, and 1988.

Region and country Year

1978 1984 1988

Europe
Czechoslovakia 2 000 2 000
France 2 000 10 000 8 000
Federal Republic
of Germany 4 000 8 000 8 000
Hungary 1 000 3 000 2 000
Others 1 000 1 200 2 000
Asia
Japan 200 13 000 12 000
China 600 5 000 5 000
United States 8 000 3 000
Others 1 000 1 000 1 000
Total 17 800 46 200 40 000

the aircraft is attacked by liquid gallium can be

reduced. In addition, there is a limit imposed on
the amount of gallium which may be carried in
an aircraft.

7. Uses
The main use of gallium is as a raw material
in the manufacture of semiconductors which are
formed by the combination of gallium with el-
ements of group 15 (especially P and As). They
have certain advantages over other semiconduc-
tor materials: (1) faster operation with lower
power consumption, (2) better resistance to ra-
diation and, most importantly, (3) they may be
used to convert electrical into optical signals.
The largest proportion of the gallium pro-
duced worldwide goes to the manufacture of
the arsenide or phosphide for the production of
lightemitting diodes (LEDs, → Display Tech-
nology; → Electroluminescent Materials and
Devices). The manufacture of integrated circuits
using gallium arsenide is still at the develop-
ment stage. A small proportion of the gallium
produced is converted into the oxide for manu-
facture of gallium – gadolinium garnets (GGG)
[8]. These are used to produce magnetic bubble
memories.
8. Economic Aspects
In 1986, 50 t gallium was used worldwide
(Fig. 2), mainly in the manufacture of light-
emitting diodes and other optoelectronic com-
ponents.
Figure 2. World gallium consumption
About 65 % of the market is in Japan, 20 %
in the United States, and 15 % in Europe. The
price has fallen continuously since 1970 and
in 1986 reached $ 450 or 77 000 yen per kg
for 6N gallium. The total value of the gallium
used worldwide in 1986 was therefore $ 22×106
(3.85×109 yen). Gallium is extracted in Western
Europe, Japan, and several countries of the East-
ern Bloc. Production levels in the Soviet Union,
the German Democratic Republic, Hungary, and
Czechoslovakia are not known exactly as only a
small part of the gallium produced there is ex-
ported.
The following companies produce gal-
lium: INGAL, (Federal Republic of Germany),
Rhône-Poulenc (France), Sumitomo (Japan),
and Dowa Mining (Japan). Musto Mining
(USA), Eagle Picher (USA), Alcan (Canada),
and Cominco (Canada) have ceased production.
6 Gallium and Gallium Compounds
In addition to these producers of primary gal-
lium, a number of companies recover pure gal-
lium from gallium scrap.
World gallium production increased from
17 800 kg in 1978 to 46 200 kg in 1984, but de-
creased to 40 000 kg in 1988 (Table 1).
9. Toxicology and Industrial
Medicine
Gallium is only slightly toxic. No industrial in-
jury caused by the metal or its compounds during
gallium production and processing has been re-
ported. An investigation in 1984 and 1985 by the
Chemical Trade Association did not reveal any
evidence of damage to health caused by gallium.
10. References
1. F. A. Cotton, G. Wilkinson: Advanced
Inorganic Chemistry, 4th ed., Wiley, New
York 1980, pp. 326 – 351.
2. Gmelin, 8, System no. 36.
3. Gmelin, Organogallium Compounds, Part 1
(1987).
4. I. A. Sheka, I. S. Clans, T. T. Mityureva: The
Chemistry of Gallium, Elsevier, Amsterdam
1966.
5. F. E. Katrak, J. C. Agarwal, J. Met. 33 (1981)
no. 9, 33.
6. Rhône-Poulenc, FR 2307 047, 1974 (J.
Helgorsky, A. Leveque).
7. Sumitomo Chem. Comp., EP 0076 404, 1983.
8. Vereinigte Aluminiumwerke AG,
DE 25 17 292, 1975, (H. Pfundt, M. Fuchs, P.
Voiß).
 Gas Chromatography 1

Gas Chromatography
Pat J. F. Sandra, University of Stellenbosch, Matieland, South Africa; Universiteit Gent, Vakgroep Organische
Chemie, Gent, Belgium

1. Introduction . . . . . . . . . . . . . . 3 6.1. Classification . . . . . . . . . . . . . 35

2. Instrumental Modules . . . . . . . 4 6.2. Universal Detectors . . . . . . . . . 36
3. The Separation System . . . . . . . 4 6.2.1. Flame Ionization Detector . . . . . . 36
3.1. Modes of Gas Chromatography . 4 6.2.2. Thermal Conductivity Detector . . . 37
3.1.1. Gas – Liquid Chromatography . . . 4 6.3. Selective Detectors . . . . . . . . . . 38
3.1.2. Gas – Solid Chromatography . . . . 4 6.3.1. Electron Capture Detector . . . . . . 38
3.2. Selection of the Carrier Gas . . . . 5 6.3.2. Nitrogen Phosphorus Detector . . . 40
3.3. Selection of the Gas Chromato- 6.3.3. Flame Photometric Detector . . . . . 40
graphic Column . . . . . . . . . . . 6 6.3.4. Overview of Other Selective Detec-
3.3.1. Packed Columns . . . . . . . . . . . . 6 tors . . . . . . . . . . . . . . . . . . . . 40
3.3.2. Capillary Columns . . . . . . . . . . . 7 6.4. Detectors Allowing Selective
3.4. Stationary Phases in Gas Chro- Recognition . . . . . . . . . . . . . . 40
matography . . . . . . . . . . . . . . 10 6.4.1. Mass Spectrometry . . . . . . . . . . 41
3.4.1. General Considerations . . . . . . . . 10 6.4.2. Fourier Transform Infrared Spec-
3.4.2. Solid Phases . . . . . . . . . . . . . . 12 troscopy . . . . . . . . . . . . . . . . . 42
3.4.3. Liquid Phases . . . . . . . . . . . . . . 14 6.4.3. Atomic Emission Detection . . . . . 44
3.4.3.1. Basic Phases for Capillary GC . . . 14 7. Practical Considerations in Qual-
3.4.3.2. Selectivity Tuning . . . . . . . . . . . 15 itative and Quantitative Analysis 46
3.4.3.3. Tailor-Made Phases . . . . . . . . . . 16 7.1. Qualitative Analysis . . . . . . . . . 46
4. Choice of Conditions of Analysis 17 7.2. Quantitative Analysis . . . . . . . . 48
4.1. Temperature-Programmed Anal- 8. Coupled Systems . . . . . . . . . . . 48
ysis . . . . . . . . . . . . . . . . . . . . 17 8.1. Multidimensional Capillary GC . 48
4.2. Constant Pressure, Constant 8.2. Multimodal High-Performance
Flow, and Pressure Programming 18 Liquid
5. Sample Inlet Systems . . . . . . . . 20 Chromatography – Capillary GC 51
5.1. General Considerations . . . . . . 20 8.3. Multimodal Supercritical Fluid
5.2. Universal Inlets . . . . . . . . . . . . 21 Extraction – Capillary GC . . . . . 53
5.2.1. Packed Column Inlets . . . . . . . . . 21 9. Applicability . . . . . . . . . . . . . . 55
5.2.2. Capillary Column Inlets . . . . . . . 21 9.1. Solute Thermal Stability . . . . . . 55
5.2.2.1. Split Injection . . . . . . . . . . . . . . 22 9.2. Solute Volatility . . . . . . . . . . . . 55
5.2.2.2. Splitless Injection . . . . . . . . . . . 23 9.3. Comparison of Gas Chromatogra-
5.2.2.3. Direct Injection . . . . . . . . . . . . . 26 phy, Liquid Chromatography, and
5.2.2.4. Cool On-Column Injection . . . . . 28 Supercritical Fluid Chromatogra-
5.2.2.5. Programmed-Temperature Injection 31 phy . . . . . . . . . . . . . . . . . . . . 56
5.3. Selective Inlets . . . . . . . . . . . . 32 10. Recent and Future Developments 59
5.3.1. Static and Dynamic Head Space 10.1. Fast High Resolution Capillary
Analysis . . . . . . . . . . . . . . . . . 33 GC . . . . . . . . . . . . . . . . . . . . 59
5.3.2. Purge and Trap Systems . . . . . . . 34 10.2. The Concept of Retention Time
5.3.3. Thermal Desorption Units . . . . . . 34 Locking . . . . . . . . . . . . . . . . . 60
5.3.4. Pyrolysis Gas Chromatography . . . 35 10.3. Towards Black Boxes . . . . . . . . 62
6. Detectors . . . . . . . . . . . . . . . . 35 11. References . . . . . . . . . . . . . . . 63

Abbreviations CI chemical ionization

CpSi cyanopropylsilicone
AED atomic emission detection
df film thickness
CGC capillary gas chromatography

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b05 181
2 Gas Chromatography
DM diffusion coefficient of the mobile
phase
dp particle diameter
ECD electron capture detector
EI electron ionization
ELCD Hall eletrolytic conductivity detector
EPC electronic pressure control
FFAP free fatty acid phase
FID flame ionization detector
FPD flame photometric detector
FSOT fused silica open tubular
GALP good automated laboratory practice
GLC gas – liquid chromatography
GLP good laboratory practice
GSC gas – solid chromatography
H column efficiency, plate height
HPLC high performance liquid chromatogra-
phy
HS head space
i.d. internal diameter
K Kelvin temperature
k retention factor
L column length
MAOT maximum allowable operating temper-
ature
MDCGC multidimensional capillary chro-
matography
MeSi methylsilicone
MiAOT minimum allowable operating temper-
ature
N plate number
NPD nitrogen phosphorus detector
PCGC packed column gas chromatography
PID photoionization detector
PLOT porous layer open tubular
PT purge and trap
PTV programmed-temperature vaporization
r column radius
RCD redox chemiluminescence detector
Rs peak resolution
SFC supercritical fluid chromatography
SFE supercritical fluid extraction
SIM selected ion monitoring
TCD thermal conductivity detector
TD thermal desorption
TEA thermal energy analyzer
TID thermionic detector
tM retention time of solvent
tR retention time of analyte
u mobile phase velocity
WCOT wall-coated open tubular
α separation factor
1. Introduction
Gas chromatography (GC) is the separation
technique that is based on the multiplicative
distribution of the compounds to be separated
between the two-phase system solid or liquid
(stationary phase) and gas (mobile phase). Gas
chromatography by definition thus comprises
all separation methods in which the moving
phase is gaseous. Contrary to the other chro-
matographic techniques, i.e., high-performance
liquid chromatography (HPLC) and supercriti-
cal fluid chromatography (SFC), the role of the
gaseous mobile phase – quasi-ideal inert gases
such as nitrogen, helium, or hydrogen – is purely
mechanical: they just serve for the transport of
solutes along the column axis. The residence
time (retention) of solutes is affected only by
their vapor pressure, which depends on the tem-
perature and on the intermolecular interaction
between the solutes and the stationary phase.
Currently, gas chromatography is one of the
most important and definitely the most eco-
nomic of all separation methods. Its applica-
bility ranges from the analysis of permanent
gases and natural gas to heavy petroleum prod-
ucts (up to 130 carbon atoms, simulated distilla-
tion), oligosaccharides, lipids, etc. Moreover, as
far as chromatographic efficiency and GC sys-
tem selectivity is concerned, no other separation
technique can compete with gas chromatogra-
phy. The dictum “If the separation problem can
be solved by gas chromatography, no other tech-
nique has to be tried out” is now generally ac-
cepted. As illustration, more than 80 % of the
priority pollutants on the lists of the EC and of
the EPA in the United States, are amenable to
GC analysis.
Gas chromatography was developed in the
early 1950s [8]. Tens of thousands of publica-
tions and more than 250 textbooks on theory
and practice have been published. The purpose
of this article is not to write a new textbook on
GC but rather to help newcomers in the field to
find their way in the present state of the art of
modern GC. For the basic aspects of GC, see
→ Basic Principles of Chromatography. Funda-
mental equations are given or repeated only to
clarify some important statements. The terms,
symbols, and nomenclature used are those that
have been advised by IUPAC [9].

At the end of the references, some general and
specialized textbooks are listed, together with
the most important journals dealing with gas
chromatography. The reader is advised to con-
sult these books and journals for a more detailed
study.
2. Instrumental Modules
A schematic drawing of a modern gas chro-
matographic system is shown in Figure 1. The
basic parts are the carrier gas supply (a), the
injector (b), the column (c), and the detector
(e). The dashed lines indicate thermostatted re-
gions. The carrier gas is usually supplied from
a high-pressure cylinder equipped with a two-
stage pressure regulator. Via the controller of
the GC instrument (f), the gas flow can be fine-
tuned, and preheated carrier gas is delivered to
the column in the constant-pressure, constant-
flow, or pressure-programmed mode. The sam-
ple is introduced into the carrier gas stream
via the injector, and the vaporized components
are transported into the column, the heart of
the system, where separation occurs. The col-
umn is placed in an oven, the temperature of
which can be kept constant (isothermal opera-
tion) or programmed (temperature-programmed
operation). Some applications are performed at
subambient temperature and instruments can be
equipped with cryogenic units. After separa-
tion, the component bands leave the column and
are recorded (g) as a function of time (chro-
matogram) by a detection device (e). The chro-
matogram provides two types of data. The res-
idence time or retention time of the compo-
nents in the column is characteristic for the
solute – stationary phase interaction and can be
used for qualitative interpretation or component
identification. The detector’s response is propor-
tional to the amount of separated sample com-
ponent and gives quantitative information on the
composition of the mixture.
3. The Separation System
3.1. Modes of Gas Chromatography
Two types of gas chromatography exist: gas –
liquid chromatography (GLC) and gas – solid
Gas Chromatography 3
chromatography (GSC). Other classification
schemes such as GSC, GLC plus capillary gas
chromatography (CGC) are outdated because
nowadays GLC and GSC can be performed both
in packed columns and in capillary or open tubu-
lar columns.
Figure 1. Basic components of a modern GC system
a) Carrier gas supply; b) Injector; c) Column; d) Column
oven; e) Detector; f ) Controller; g) Recorder
3.1.1. Gas – Liquid Chromatography
In GLC the stationary phase is a liquid acting as
a solvent for the substances (solutes) to be sep-
arated. The liquid can be distributed in the form
of a thin film on the surface of a solid support,
which is then packed in a tube (packed column
GC, PCGC) or on the wall of an open tube or
capillary column (capillary GC, CGC). The term
WCOT (wall-coated open tubular) is used only
for capillary columns coated with a thin film of
a liquid. In GLC the separation is based on parti-
tion of the components between the two phases,
the stationary phase and the mobile phase, hence
the term partition chromatography. This mode of
GC is the most popular and most powerful one.
3.1.2. Gas – Solid Chromatography
Gas – solid chromatography comprises the tech-
niques with an active solid as the stationary
phase. Separation depends on differences in
adsorption of the sample components on in-
organic adsorbents (i.e., silica, alumina, car-
bon black) or on organic adsorbents such as
styrene – divinylbenzene copolymers. Separa-
tion can also occur by a size exclusion mecha-
nism, such as the separation of gases on synthetic
4 Gas Chromatography
zeolites or molecular sieves. GSC is performed
on packed columns or on open tubular columns
on the walls of which a thin layer of the porous
material is deposited [ porous layer open tubu-
lar (PLOT) columns]. GSC nowadays is used
only for special separation problems, and GSC
columns are, therefore, referred to as tailor-made
columns.
3.2. Selection of the Carrier Gas
Common carrier gases are nitrogen, helium, and
hydrogen. The choice of carrier gas depends on
the column and the detector used but, above
all, on the required speed of analysis and de-
tectability. The influence of the mobile-phase
velocity u on column efficiency H has been de-
tailed in → Basic Principles of Chromatogra-
phy. The relation H – u was derived for packed
column GC by Van Deemter, Zuiderweg,
and Klinkenberg [10] and adapted to capillary
columns by Golay [11]. Practical consequences
of the carrier gas selection in capillary GC have
been described in [12], [13]. Due to the relatively
high density of nitrogen compared to helium and
hydrogen, longitudinal diffusional spreading of
the solutes in nitrogen is small, but the resistance
to mass transfer in the mobile phase is high.
In contrast, for low-density gases such as he-
lium and especially hydrogen, longitudinal dif-
fusional spreading is large but resistance to mass
transfer small. For columns with small amounts
of stationary phases, the resistance to mass trans-
fer in the stationary phase can be neglected, and
the minimum plate height H min is nearly inde-
pendent of the nature of the carrier gas. The opti-
mum mobile-phase velocity uopt , corresponding
to H min is proportional to the diffusion coeffi-
cient of the mobile phase DM ; uopt is 10 cm/s
for nitrogen, 25 cm/s for helium, and 40 cm/s for
hydrogen. In practical GC on thin-film columns,
hydrogen is the best choice because the analysis
time is reduced by a factor of 4 compared to ni-
trogen, while the detectability is increased by the
same order. Some experimental H – u curves for
a capillary column 20 m in length and 0.27 mm
internal diameter (i.d.) coated with a 0.22-µm
film of methylsilicone (MeSi) are shown in Fig-
ure 2. The experimental data fit the theory per-
fectly. The fact that the slope (i.e., the increase
of plate height with velocity) for nitrogen is
much steeper than for the two other gases is
noteworthy. Working close to uopt is, therefore,
a must with nitrogen, whereas for helium and
hydrogen the velocity can be increased to val-
ues greater than uopt without losing too much
resolution power. For thin-film columns, hydro-
gen is definitely the best choice. When hydro-
gen is not allowed for safety reasons – most GC
systems nowadays are equipped with hydrogen
sensors – helium should be chosen. Because of
the important contribution of the resistance to
mass transfer in thick-film columns, this situa-
tion is more complicated. The selection depends
on what is considered most important, efficiency
or speed. This is dictated by the separation prob-
lem at hand. For a given column, the selection
of carrier gas and optimum flow rate is best de-
termined experimentally by making H – u plots.
This is not difficult and can be carried out in
3 – 4 h in the following way:
1) A solution of a hydrocarbon (i.e., tridecane)
in a highly volatile solvent (i.e., hexane) is
injected at an inlet pressure Px of carrier gas
A and a column temperature is selected to
give a retention factor k of ca. 5.
2) The plate number N is calculated according
to
N = 5.54 (tR /wh )2 (3.1)
where t R is the retention time of the hy-
drocarbon and wh is the peak width at half
height.
3) The H value is calculated from
H =L/N (3.2)
where L denotes the column length.
4) The corresponding u value is given by
u=L/tM (3.3)
where t M is the retention time of the solvent;
for thick-film columns, methane is injected
instead of hexane to give t M .
5) The H and u values corresponding to Px
of carrier gas A are marked in a H – u plot
(Fig. 3).
6) The inlet pressure P is set at values Px −3 ,
Px −2 , Px −1 , Px +1 , Px +2 , Px +3 , and the cor-
responding H and u values are drawn in the
plot.

7) H min and uopt are deduced from the plot.
8) The same procedure is repeated for carrier
gases B and C.
Figure 2. Experimental H – u curves as function of carrier
gas
Figure 3. Making a H – u plot
Gas Chromatography 5
High-purity gases should be used in GC.
Most gas suppliers have special GC-grade gases.
If lower quality carrier gases are used, purifica-
tion through a molecular sieve trap to remove
moisture and low molecular mass hydrocarbons
and through an oxytrap to remove oxygen is rec-
ommended.
3.3. Selection of the Gas
Chromatographic Column
Two column types are in use, the packed and
the capillary column. The selection is often dic-
tated by the nature and complexity of the sample.
The present trend is to replace PCGC by CGC
whenever possible, because data obtained with
the latter technique are much more reliable. The
fundamental difference between the two meth-
ods is reflected in the resolution equation, the
key equation for separation optimization:
√
N α−1 k
RS = (3.4)
4 α k+1
Anything that increases the column efficiency N,
the column selectivity α, or the retention factor k
will enhance the separation power of the column.
Packed columns are characterized by low plate
numbers and PCGC is therefore a low-resolution
technique. The lower efficiency is compensated
by the high selectivity α of the stationary phase,
and this is the main reason why so many dif-
ferent stationary phases have been developed
for PCGC. Capillary columns on the other hand
have very high plate numbers and, therefore, the
number of stationary phases can be restricted
because the selectivity is less important. In fact,
most separation problems can be handled with
four basic stationary phases and half a dozen
tailor-made stationary phases. Other important
features of capillary columns are their inertness
and compatibility with spectroscopic detectors.
In the framework of this discussion, emphasis
is, therefore, on capillary columns.
3.3.1. Packed Columns
A packed column is defined by the material of
which the tube is made, by its length L and
internal diameter i.d., by the nature and diam-
eter d p of the particles, and of course by the
6 Gas Chromatography
film thickness d f and the nature of the sta-
tionary phase. The latter is most important be-
cause the stationary phase controls column se-
lectivity (see Section 3.4). All other column pa-
rameters represent column efficiency. In packed
column GC, H min is controlled mainly by the
particle diameter and is always >2d p . A col-
umn 1 m long filled with particles of 100 – 120
mesh (150 – 125 µm) can never generate more
than 3000 plates. Because of the packed bed,
the resistance to the mobile flow is high, and
columns longer than 3 m exhibit low permeabil-
ity and are not practical. This means that a to-
tal plate number of 10 000 is the maximum that
can be reached with packed columns. Most of
the columns for routine analysis in fact have
only 3000 to 5000 plates. The column efficiency
is independent of column diameter. The col-
umn tube can be made of copper, stainless steel,
nickel, glass, and polytetrafluoroethylene. Glass
and polytetrafluoroethylene are the most inert
materials and are preferred for the analysis of
polar and thermolabile compounds. In gas – liq-
uid chromatography, the support material has
a silicon oxide network, such as diatomaceous
earth, synthetic spherical silica, or glass beads.
The support materials are purified by acid wash-
ing and deactivated by silanization, which caps
the active sites. However, even the most highly
deactivated surface will still exhibit adsorption
of polar compounds such as organic acids and
bases. A variety of support materials are avail-
able commercially, the catalogues of the column
manufacturers (Agilent, Chrompack, Supelco,
Alltech, etc.) should be consulted for detailed
information. The stationary-phase film is homo-
geneously coated on the particles by dissolving
the phase in a suitable solvent and adding the
support material to the mixture. The solvent is
then removed on a rotavapor (rotary evapora-
tor), and after complete drying under a purified
nitrogen flow, the column is packed tightly with
the coated support. In PCGC, the contents of liq-
uid coatings are expressed as a percentage of the
support material: 1, 3, 5, and 10 wt % are com-
monly used.
The dimensions of columns used in
gas – solid chromatography are very similar to
those of gas–liquid chromatography. Packing
materials (silica, alumina, carbon blacks, zeo-
lites, porous polymers) in proper mesh size are
available commercially to fill the columns. GSC
columns give lower plate numbers than GLC
columns but possess very high selectivities for
some typical applications. Prepacked GLC and
GSC columns can be purchased commercially
and are ready to be installed in the GC instru-
ment.
3.3.2. Capillary Columns
Major progress in gas chromatography, particu-
larly in the area of applications, has been made
by the introduction of capillary columns. In-
vented by M. Golay in 1957 [11], the real break-
through came only in 1979 with the development
of flexible fused silica as tubing material for cap-
illary columns [14] (fused silica open tubular
columns, FSOT). The inherent strength and flex-
ibility of fused silica made use of capillary GC
easy, compared to the glass capillary columns
generally used previously. In addition, no other
column material can offer the same inertness.
A capillary column is characterized by its di-
mensions (L, i.d.) and by the nature of the sta-
tionary phase. For GLC, a relatively thin sta-
tionary (liquid) phase film, with film thickness
d f , is coated directly on the inner wall (WCOT
columns). The film thickness controls the reten-
tion factor k and the sample capacity of a capil-
lary column. In the case of GSC, the adsorbent
with particle diameter d p is deposited in a thin
layer d l on the capillary wall (PLOT columns).
The main advantage of PLOT columns com-
pared to packed GSC columns is the speed of
analysis (see Section 3.4.2). Most of the applica-
tions (> 90 %) in capillary GC are performed on
WCOT columns. These columns can be subdi-
vided in three types according to their internal di-
ameter. Columns with i.d. of 0.18 – 0.32 mm are
called conventional capillary columns because
this is the column type most often used for the
analysis of complex samples. Columns with an
i.d. of 0.53 mm are known as widebore or mega-
bore columns. They have been introduced as an
alternative to packed columns for the analysis
of less complex mixtures. Narrowbore columns
with i.d.’s ranging from 0.1 to 0.05 mm provide
very high efficiencies or short analysis times.
This column type is not often used nowadays,
but this situation is expected to change in the
next few years (see Section 10.1).
 Gas Chromatography 7

The selection of a capillary column depends ≈0.1 µm high molecular mass compounds 500 – 1500
on the complexity of the sample to be ana- ≈0.2 µm M r ≈ 300 – 500
lyzed. The column length, the internal diame- ≈0.3 µm M r ≈ 150 – 400
ter, the stationary phase, and its film thickness ≈0.5 µm M r ≈ 50 – 200
≈1 µm M r ≈ 30 – 150
determine the separation power (resolution), the 2 – 5 µm widebore – high-capacity
sample capacity, the speed of analysis, and the narrowbore – high volatiles
detectability or sensitivity. Theoretical consid-
erations [12], [13] indicate that for capillary
columns with thin films (<1 µm), the H min value Table 1. Characteristics of FSOT columns coated with thin films
is roughly equal to the column diameter. This
dc, H min , N, m−1 L for
is illustrated in Figure 4, which shows experi- mm mm 100 000
mental H – u curves for columns varying in in- plates, m
ternal diameter. H was calculated for dodecane
at 100 ◦ C with hydrogen as carrier gas. H min
0.05 0.05 20 000 5
0.10 0.10 10 000 10
measured experimentally is indeed very close to 0.18 0.18 5 556 18
H min deduced theoretically. By knowing this, 0.22 0.22 4 545 22
0.25 0.25 4 000 25
the maximum plate number that a capillary col-
0.32 0.32 3 125 32
umn can provide may be calculated without per- 0.53 0.53 1 887 53
forming any analysis:

N =L/H =L/Hmin =L/dc (3.5)

The H min values, the maximum number of

plates per meter, and the minimum column
length needed for 100 000 plates for different
i.d.’s of commercially available FSOT columns
are listed in Table 1. In contrast to packed
columns, the length of a capillary column is not
restricted because the permeability of an open
tube is very high. To a great extent, the length and
internal diameter of a capillary column define
the efficiency. The selection of the film thickness
for a given stationary phase is also of upmost
importance. The resolution equation (Eq. 3.4)
shows that low k values result in poor resolu-
tion. For the same column efficiency N and se-
lectivity α, increasing the k value from 0.25 to Figure 4. Experimental H – u curves for columns with
5 corresponds to a resolution gain of 378 % (Rs different i.d.’s
increases from 0.37 to 1.40). Increasing the re- a) 0.88 mm; b) 0.70 mm; c) 0.512 mm; d) 0.27 mm;
e) 0.18 mm
tention factor can be accomplished by increasing
the film thickness
Conventional Capillary Columns. Capil-
K 2df
k= (3.6) lary columns with i.d.’s of 0.18 – 0.32 mm and
rc
lengths of 10 – 60 m are the “workhorses” for
For a fixed column radius (r c = constant), the high-resolution separation. Long columns are
retention factor of a solute at a given tempera- preferred for the analysis of very complex sam-
ture (K = constant), doubles when the film thick- ples. The less complex the sample, the shorter
ness is increased by a factor of 2. Guidelines for the column can be. Figure 5 shows the analy-
the selection of film thickness for the stationary sis of the oxygen fraction of the essential oil
phase methylsilicone are listed below (values de- of black pepper [15]. The profile is extremely
pend on column length and stationary phase) : complex (more than 300 compounds), and the
column efficiency must be high to unravel all
8 Gas Chromatography
Figure 5. Analysis of oxygen-containing compounds of essential oil of pepper
Column: 40 m L×0.25 mm i.d.; 0.25 µm d f high molecular mass poly(ethylene glycol); temperature as indicated; split injection
1/50; carrier gas hydrogen at 15 psi (≈1 bar); FID
solutes. Long columns, of course, imply long
analysis times. Figure 6 shows the carbon num-
ber separation of the neutral lipids in palm oil.
The separation is less challenging and the col-
umn length can be reduced to 5 m, which results
in an analysis time of only 3 min [16]. For sam-
ples of unknown complexity, column lengths of
25 – 30 m offer a good compromise. Column di-
mensions are often adapted to the requirements
of pre- or postcolumn devices. As an example,
for the combination with mass spectroscopy, an
internal diameter of 0.18 – 0.25 mm is preferred
because in this case the flow of the mobile phase
is of the order of 1 mL/min. This flow rate fits
well with the pump capacity of the spectrometer
so that special interfacing is not required.
Widebore Capillary Columns. FSOT cap-
illary columns with i.d.’s of 0.53 mm were in-
troduced as alternatives to packed columns,
with the inertness of fused silica as their main
advantage. Widebore or megabore columns
have higher sample capacities and are appli-
cable for simple packed column-like separa-
tions. A serious limitation of small i.d. capil-
lary columns indeed is the low sample capacity
(25 m L×0.25 mm i.d.; d f = 0.2 µm results in a
capacity of roughly 20 ng per compound). Sam-
ple capacity is the ability of a column to tol-
erate high concentrations of solutes. If the ca-
pacity is exceeded, the chromatographic per-
formance is degraded as evidenced by leading
(overloaded) peaks. Sample capacity is related
to the film thickness and column radius. A col-
umn of 10 m×0.53 mm, d f = 1 µm, has a sam-
ple capacity >200 ng per compound. Simple in-
let devices can be used with widebore columns
in the low-resolution mode. In this mode, the
carrier gas velocity is far above optimum val-
ues (flows of 8 – 12 mL/min), and a 10-m col-
umn generates only 5000 – 8000 plates. For sim-
ple mixtures, these efficiencies are sufficient.
Megabore columns are also available in lengths
of 30 – 60 m. At optimum velocities (flows of
1 – 3 mL/min) they offer 50 000 and 100 000
plates, respectively, which is considered high-
resolution GC.
Narrowbore Capillary Columns. Narrow-
bore columns offer very high efficiencies (100 m
L×0.1 mm i.d. = 1 000 000 plates) or ultrahigh
speed at 100 000 plates but at the expense of
sample capacity. This is illustrated in Figure 7
for the analysis of fatty acid methyl esters on
a 10 m L×0.1 mm i.d., d f 0.1 µm, column of
cyanopropylsilicone (CpSi). Total analysis time
is only 90 s. Sample injection is critical because
the sample capacity is <1 ng. This is the reason
for the slow acceptance of narrowbore columns.
Normal sample size injection is expected to be
possible with the development of new sample
 Gas Chromatography 9

inlets such as programmed temperature vapor-

ization in the solvent venting mode.

Figure 6. Fast separation of palm oil

Figure 7. Fast separation of fatty acid methyl esters
Column: 5 m L×0.25 mm i.d.; 0.1 µm d f methylsilicone;
Column: 10 m L×0.1 mm i.d.; 0.1 µm d f cyanopro-
temperature: 290 – 350 ◦ C at 30 ◦ C/min; cool on-column in-
pylsilicone; temperature: 180 ◦ C; split injection 1/500; car-
jection; carrier gas hydrogen at 15 psi (≈1 bar); FIDPeaks:
rier gas hydrogen at 60 psi (≈ 4 bar); FID
32 – 36 diglycerides, 46 – 56 triglycerides
Peaks: as indicated (the figure before the colon denotes the
number of carbon atoms; that after the colon, the number of
double bonds per molecule)

3.4. Stationary Phases in Gas

Chromatography

3.4.1. General Considerations

The importance of the stationary phase in GC

can, once again, be deduced from the resolution
equation (Eq. 3.4). In Figure 8, the influence of
the plate number N, the separation or selectivity
factor α, and the retention factor k on peak res-
olution Rs is represented graphically. The peak
resolution of two solutes (k = 5) with α = 1.05 on
a column with a plate number of 20 000 (e.g.,
10 m×0.5 mm coated with 0.2 µm methylsili-
cone) is 1.4. This value, the crossing point of
Figure 8. Effect of N, α, and k on Rs
the curves, is taken as reference. The curves are
obtained by changing one of the variables while
the other two remain constant. From the curves, Plate Number N. Peak resolution is propor-
the following conclusions can be drawn: tional to the square root of the plate number.
10 Gas Chromatography
Increasing the plate number by a factor of 2
(N = 20 000 to N = 40
√ 000) improves peak reso-
lution by only 1.4 ( 2 gives Rs = 1.40 → 1.96).
Retention Factor k. For values > 5, the in-
fluence of k on Rs is small. Increasing k from 5 to
20 increases resolution by only 14 % (Rs = 1.40
→ 1.60).
Separation Factor α. Optimization of the
separation factor has the most important im-
pact on peak resolution. Increasing α from
1.05 to 1.10 nearly doubles the peak resolu-
tion (Rs = 1.40 → 2.68), while a slight decrease
(α = 1.03) causes a drastic loss of resolution
(Rs = 1.40 → 0.86). The selection of a “liquid
phase” that maximizes the relative retention of
solutes is thus of upmost importance. The x-
scales in Figure 8 have not been selected arbi-
trarily. Varying plate number and retention fac-
tor, respectively, from N = 20 000 to 40 000 and
from k = 5 to 20 is not so difficult to realize. In
contrast, increasing the separation factor is not
easy to achieve, especially in gas chromatogra-
phy. First of all, as already mentioned, the mo-
bile phase is an inert gas and its role is purely
mechanical. Second, optimization of the selec-
tivity of the stationary phase for a particular sam-
ple means that the nature of the solutes must be
known. Optimization then requires good chem-
ical insight and intuition. Several separations
have been achieved more by luck than by skill.
In 1991 a book was published with very detailed
discussion of practically every stationary phase
used since the inception of gas chromatography
[17]. The reader is referred to this book for more
information.
The selectivity of a stationary phase is com-
monly expressed in terms of the relative reten-
tion of a compound pair:
α=k2 /k1 (3.7)
The thermodynamic description of Equa-
tion (3.7) is
α=p◦1 /p◦2 .γ1◦ /γ2◦ (3.8)
◦ very high efficiency of a capillary column. Even
where p refers to the saturated vapor pres-
sure of the analyte and γ ◦ is the activity of
the analyte at infinite dilution in the station-
ary phase. Equation (3.8) is split in two contri-
butions: the first term is related to the solutes
and depends only on temperature, whereas the
second term depends on the selective proper-
ties of the stationary phases. Solute – stationary
phase interactions are very complex and
may include nonspecific interactions (disper-
sion interactions); specific interactions such as
dipole – dipole, dipole – induced dipole, and hy-
drogen bonds; and chemical interactions such
as acid – base, proton donor – proton acceptor,
electron donor – electron acceptor, and inclu-
sion. The terms selectivity and polarity are
commonly used to describe a stationary phase.
A polarity and selectivity scale of more than
200 stationary phases has been established by
McReynolds [18]. The Kovats retention in-
dices (see Chap. 7) of benzene, butanol, 2-
pentanone, nitropropane, and pyridine on phase
X are measured, and the differences in indices
in phase X, relative to the stationary phase
squalane as typical apolar phase, are listed in-
dividually (selectivity) and as a sum (polar-
ity). Although the polarity scale is discussed
in all textbooks on GC, it has little practical
value. The following are by far the most com-
mon methods used for selection of a station-
ary phase: trying a phase with good chromato-
graphic properties, looking for a similar appli-
cation that has already been published, or ask-
ing a colleague with experience (trial and er-
ror) for advice. At this stage the difference bet-
ween PCGC and CGC should be restressed.
Consider a packed column and a capillary col-
umn coated with the same stationary phase
of the following characteristics: packed col-
umn, 2 m L×4 mm i.d., packed with 100 – 120
mesh diatomaceous earth particles, 3 % methyl-
silicone, plate number 5000; capillary col-
umn, 25 m L×0.25 mm i.d., coated with 0.25 µm
methylsilicone, plate number 100 000. By ne-
glecting the k contribution in the resolution
equation, the resolution for two solutes with
different α values can be calculated (Table 2).
For an α value of 1.05, the resolution on the
packed column is insufficient and another sta-
tionary phase must be selected. On the capillary
column for the same solute – stationary phase in-
teraction the resolution is still 3.6 because of the
for α values of 1.02, baseline separation is ob-
tained. In the case of α value 1.01, the resolution
is only 0.8, but due to the high permeability of
a capillary column, its length can be increased

to provide the required plate number N req on
the same stationary phase. From the resolution
equation follows:
Nreq = 16Rs2 (α/α−1)2 = 160000plates (3.9)
and as N = L/d c , the required length for Rs = 1 is
40 m. The analysis of a fatty acid methyl ester
mixture on a packed column with a highly se-
lective phase for these solutes (ethylene glycol
succinate) is shown in Figure 9; several peaks are
incompletely separated. The same analysis was
performed on a capillary column coated with
poly(ethylene glycol), a stationary phase with
no particular selectivity for the solutes (Fig. 10) :
all peaks are baseline separated.
Table 2. Resolution Rs for different α values
3.4.2. Solid Phases
For certain applications, GSC enjoys some ad-
vantages over GLC. Adsorbents are stable over
awide temperature range, and column bleed is
virtually nonexistent especially for inorganic ad-
sorbents and molecular sieves. Silica and alu-
mina adsorbents give excellent separation of sat-
urated and unsaturated hydrocarbons with low
molar mass. Medium-polarity and polar solutes
interact too strongly with the highly adsorptive
surface of these adsorbents. Graphitized carbon
blacks are well suited for separation of structural
and geometric isomers. The disadvantage of car-
bon blacks is that their retention characteristics
differ from batch to batch and they seem difficult
to prepare in a reproducible way. Inorganic ad-
sorption columns can be modified by coating the
material with a small amount of nonvolatile liq-
uid or inorganic salt. The most adsorptive sites
Gas Chromatography 11
will bind preferentially to these modifiers. As a
result, the sites are unavailable to participate in
retention, and retention times generally decrease
with increased reproducibility. Molecular sieves
(zeolites) are aluminosilicates of alkali metals.
The most common types for GC are molecular
sieves 5A and 13X. Separation is based mainly
on the size of the solutes and the porous structure
of the molecular sieve, although adsorptive in-
teractions inside and outside the pores may also
contribute. Molecular sieves are used primarily
for the separation of permanent and inert gases
including low molar mass hydrocarbons. Porous
polymer beads of different properties have found
many applications in the analysis of volatile in-
organic and organic compounds. The properties
of the commercially available materials vary by
chemical composition, pore structure, and sur-
face area. Compared to inorganic adsorbents,
polymer beads are stable to water injections, and
on some of the materials, polar solutes give per-
fect peak shapes in reasonable analysis times.
The best-known adsorbents are the Porapak se-
ries, the Chromosorb 101-108 series, and Tenax.
The range of applications on those polymers can
be found in catalogues of the column and instru-
ment manufacturers. Tenax (a linear polymer
of para-2,6-diphenylphenylene oxide) is some-
what unique because of its thermal stability up
to 380 ◦ C. Relatively high molecular mass po-
lar compounds such as diols, phenols, or etha-
nolamines can be analyzed successfully. Some
doubt exists as to the mechanism of retention
on Tenax. At low temperature, adsorption ap-
pears to be the principal retention mechanism,
but at higher temperature the surface structure
becomes liquid-like and partitioning does occur.
Solid Phases for PLOT Columns. At the
moment, GSC is enjoying a revival because
of the introduction and commercialization
of PLOT columns. The advantages of these
columns are higher efficiency, speed of analy-
sis, and better stability and reproducibility over
time [19]. To date, PLOT columns are avail-
able in different lengths and internal diameters,
with aluminum oxide – KCl for the separation
of saturated and unsaturated hydrocarbons in-
cluding low-volatile aromatics; with molecular
sieve 5A for the analysis of permanent and inert
gases; with porous polymers of the Porapak-type
(Q,S,U) ( PoraPlot columns) for the analysis of
12 Gas Chromatography

Figure 9. Isothermal analysis (200 ◦ C) of fatty acid methyl esters on a packed column with stationary phase ethylene glycol
succinate (EGS-X)
1. C16 : 0; 2. C16 : 1; 3. C17 : 0; 4. C18 : 0; 5. C18 : 1; 6. C18 : 2; 7. C18 : 3; 8. C20 : 0; 9. C20 : 1; 10. C20 : 4; 11. C20 : 5;
12. C22 : 0; 13. C22 : 1; 14. C23 : 0; 15. C22 : 6; 16. C24 : 0; 17. C24 : 1

Figure 10. Isothermal analysis (200 ◦ C) of fatty acid methyl esters on a capillary column with high-M r poly(ethylene glycol)
as stationary phase (for designation of peaks, see Fig. 9)
 Gas Chromatography 13

Figure 11. Natural gas analysis on an Al2 O3 PLOT column

Column: 25 m L×0.25 mm i.d.; Al2 O3 – KCl; temperature: 75 – 200 ◦ C at 3 ◦ C/min; split injection; carrier gas nitrogen at 5
psi (≈3.5×104 Pa); FID

polar solutes and water; and with carbon black (
CarboPlot columns) for volatile apolar solutes in
petroleum products and environmental samples.
Figure 11 shows the determination of benzene
and toluene in natural gas on an Al2 O3 – KCl
PLOT column. The elution of benzene from
the C6 group and of toluene from the C7 group
illustrates the high selectivity.
3.4.3. Liquid Phases
In the past, numerous phases were used
in PCGC, leading to what has been called
“stationary-phase pollution” [20]. In the begin-
ning, the many phases were a blessing; later, a
curse. Today most separations are performed on
a dozen preferred phases, which are all specially
synthesized for GLC purposes. Some popular
PCGC phases, listed according to increasing po-
larity, are
– Methylsilicone (gum)
– Methylsilicone (fluid)
– Methylphenyl(5 %)silicone
– Methylphenyl(50 %)silicone
– Methyltrifluoropropyl(50 %)silicone
– Methylphenyl(25 %)cyanopropyl(25 %)silicone
– Poly(ethylene glycol), M r > 40 000
– Cyanopropyl(50 %)phenylsilicone
– Poly(ethylene glycol) esterified with 2-
nitroterephthalic acid
– Diethylene glycol succinate
– Cyanopropyl(100 %)silicone
– Ethylene glycol succinate
– 1,2,3-Tris(2-cyanoethoxy)propane
Of this list, by far the most important group
are the silicones. The reasons can be summa-
rized as follows: Their diffusion coefficients are
high, and thus resistance to mass transfer is low,
silicones have a high thermal stability (methyl-
silicone gum up to 400 ◦ C) and are liquids or
gums at low temperature, the structure is well
defined, and the polymers are very pure. For
practical GC this results in a broad temperature
range, which is defined by the minimum allow-
able operating temperature range (MiAOT) and
by the maximum allowable operating tempera-
ture range (MAOT), and low column bleeding.
Poly(ethylene glycol) with high molecular mass,
which has a unique selectivity, is a solid be-
low 60 ◦ C (MiAOT = 60 ◦ C) and bleeds at 240 –
250 ◦ C as a result of the higher vapor pressure
compared to silicones.
3.4.3.1. Basic Phases for Capillary GC
As already mentioned, the number of phases in
CGC can be reduced further due to the high ef-
ficiency those columns offer. Stark et al. [21]
studied stationary-phase characteristics in depth
and concluded that the order of optimized phases
14 Gas Chromatography
for CGC, all higher molecular mass crosslink-
able gums, is
– Methylsilicone
– Methylphenyl(50 – 70 %)silicone
– Methylcyanopropylsilicones with medium
(25 – 50 %) and high (70 – 90 %) cyanopro-
pyl content
– Methyltrifluoropropylsilicone
– High molecular mass poly(ethylene glycol)
or a silicone substitute having the same po-
larity and selectivity
Figure 12. Structures of the basic phases for capillary GC
The functionalities in those phases are
the methyl, phenyl, cyano, trifluoro, and
hydroxy – ether group, respectively. The similar-
ity with HPLC phases is remarkable. Based on
the above, Sandra et al. [22] proposed five basic
phases for capillary GC. The formulas are given
in Figure 12. For the majority of high-resolution
separations, these stationary phases provide
more than adequate performance. For some
applications, the functionalities are combined
on the same siloxane backbone, or columns are
coupled (selectivity tuning). Functionalities can
also be modified to provide specific interactions.
Optical phases and liquid crystals complete the
set of preferred CGC phases. These tailor-made
phases are discussed in Section 3.4.3.3.
The most important phase is methylsili-
cone. Separations occur according to the boil-
ing point differences of the solutes. A typi-
cal chromatogram is shown in Figure 13. Fatty
acid methyl esters are separated according
to their boiling point or molar mass. Hardly
any separation occurs among oleic (C18 : 1
cis), elaidic (C18 : 1 trans), linoleic (C18 : 2)
and linolenic (C18 : 3) acids. Methylphenylsil-
icone is the second most widely used station-
ary phase. Selectivity is increased due to the
polarizable phenyl group. Methyltrifluoropro-
pylsilicone possess rather unique selectivity for
electron donor solutes such as ketones and ni-
tro groups. Incorporating the cyano group with
its large dipole moment into the silicone back-
bone provides strong interactions with dipolar
solutes and unsaturated bonds. Cyano phases are
widely used for the separation of unsaturated
fatty acid methylesters and for the resolution
of dioxins and furans. Figure 14 represents the
analysis of a sample whose composition is very
similar to that in Figure 13. Separation accord-
ing to the number of double bonds in the alkyl
chains is due to π – π interactions. Methyl oleate
(cis C18 : 1) and methyl elaidate (trans C18 : 1)
differing only in configuration are baseline sep-
arated as well. High molecular mass poly(ethyl-
ene glycol ) has a unique selectivity and polarity
for the separation of medium-polarity and polar
compounds. The most popular of these phases
is Carbowax 20 M with average M r of 20 000.
3.4.3.2. Selectivity Tuning
A solvent with a selectivity intermediate to the
selectivities of the five basic phases can, for
some applications, offer a better separation or
a shorter analysis time. This is illustrated by the
following example. On stationary phase X, com-
pounds A and B can be separated from C, but
they cannot be separated from each other. On an-
other stationary phase Y , A and B are separated,
but one of them coelutes with C. By using a chro-
matographic system with selectivity between X

Figure 13. Analysis of fatty acid methyl esters on methylsilicone
Column: 25 m L×0.25 mm i.d.; 0.25 µm d f MeSi; temperature: 100 – 220 ◦ C at 3 ◦ C/min; split injection 1/100; carrier gas
hydrogen at 8 psi (≈5.6×104 Pa); FID
(For designation of peaks, see Fig. 7)
and Y , an optimum can be found to separate the
three compounds. Intermediate selectivities and
polarities can be obtained by selectivity tuning
[23]. Selectivity tuning means that the selectiv-
ity is adapted to the analytical need by creating a
selectivity between two (or more) extreme (basic
phase) selectivities. In principle, this can be per-
formed in three different ways: (1) by synthesiz-
ing a tuned phase with predetermined amounts
of monomers containing the required functional
groups; (2) by mixing, in different ratios, two
or three basic phases in one column; and (3)
by coupling two or more columns of extreme
selectivities. Approach (1) and (2) have been
commercially used, and columns are available
for specific applications. Columns tuned for the
analysis of classes of priority pollutants are best
known. Method (3) is detailed in Section 8.1.
3.4.3.3. Tailor-Made Phases
The most widely used tailor-made phases are
the free fatty acid phase (FFAP), liquid crys-
Gas Chromatography 15
tals, and the optical phases Chirasil-Val and
derivatized cyclodextrins. FFAP is produced by
condensing 2-nitroterephthalic acid with Car-
bowax 20M. The phase is recommended for the
analysis of acidic compounds such as organic
acids and phenols. The phase is not suitable for
the analysis of alkaline compounds and aldehy-
des with which it reacts. Liquid crystals can sep-
arate isomers as a function of the solute length-
to-breadth ratios. High selectivities have been
noted for the separation of polycyclic aromatic
compounds and dioxin isomers [24]. The most
powerful involves the use of a liquid-crystal col-
umn as second column in a multidimensional
CGC system. Optical isomers (enantiomers) can
be separated principally by two different ap-
proaches. Enantiomeric mixtures containing a
reactive group can be derivatized with an opti-
cally pure reagent to produce a mixture of di-
astereomers that can be separated on nonopti-
cally active stationary phases such as methyl-
silicone. The direct separation on optically ac-
tive stationary phases is, however, the current
method of choice because it has certain ad-
16 Gas Chromatography
vantages. Derivatization agents of 100 % enan-
tiomeric purity are not needed, and the method
can be applied to enantiomers lacking reactive
functional groups. In Chirasil-Val a diamide is
incorporated into a silicone backbone, and sep-
aration occurs via a triple hydrogen interac-
tion. A number of derivatized α-, β-, and γ-
cyclodextrin stationary phases have been intro-
duced for the separation of enantiomeric pairs.
Separation is based on the formation of inclu-
sion complexes with the chiral cavity of the cy-
clodextrins. However, none of the phases is uni-
versally applicable, and enantiomer separation is
still based on trial and error. The separation of γ-
and δ-lactones on a 2,3-O-acetyl-6-tert-butyldi-
methylsilyl-β-cyclodextrin stationary phase is
shown in Figure 15. Full details on the separa-
tion of enantiomers by capillary GC can be found
in [25], [26].
Figure 14. Analysis of fatty acid methyl esters on a
cyanopropylsilicone
Column: 25 m L×0.25 mm i.d.; 0.25 µm d f CPSi; temper-
ature: 187 ◦ C; split injection 1/100; carrier gas hydrogen at
8 psi (≈ 5.6×104 Pa); FID
4. Choice of Conditions of Analysis
Under isothermal and constant-flow conditions,
for a homologous series of hydrocarbons, an
exponential correlation exists between the res-
idence time in the stationary phase (adjusted re-
tention time) and the solute vapor pressure, boil-
ing point, or number of methylene groups (car-
bon number).
logtR =aCn +b (4.1)
where t  R is the adjusted retention time; Cn
is the number of carbons in the individual ho-
mologues; and a, b are constants. For a mix-
ture with boiling point range of the solutes less
than 100 ◦ C, an optimum isothermal tempera-
ture can be selected. For samples in which the
boiling point difference of the solutes exceeds
ca. 100 ◦ C, working in the isothermal mode is
impractical. Usually, early eluting peaks will
show poor resolution (low k values), whereas
late eluting peaks will be broad when a compro-
mise temperature has been chosen. The problem
can be solved by temperature or flow program-
ming.
4.1. Temperature-Programmed Analysis
In temperature-programmed analysis, a con-
trolled change of the column temperature oc-
curs as a function of time. The initial tempera-
ture, heating rate, and terminal temperature must
be adjusted to the particular separation prob-
lem. The initial temperature is chosen so that
the low-boiling compounds are optimally sep-
arated (k value > 3). Selection of the program
rate depends on the nature of the solutes and
the complexity of the sample. The final temper-
ature is adjusted to give reasonable total anal-
ysis times. Temperature programming has been
applied since the beginning of gas chromatog-
raphy (1960), but only since the end of the
1980s have the possibilities been fully exploited.
This might be, in part, because of the time-
consuming nature of temperature optimization
by trial and error, but above all because of ig-
norance of the importance of the temperature
programming rate to selectivity. This is espe-
cially so for polar columns where ∆t R /∆T is
much more pronounced than on apolar columns.
Today, software is available to optimize a tem-
perature program for a particular separation on
the basis of only two experimental programmed
runs. The theory of temperature-programmed
 Gas Chromatography 17

Figure 15. Enantioselective separation of γ- and δ-lactones on 2,3-O-acetyl-6-tert-butyldimethylsilyl-β-cyclodextrin

Column: 25 m L×0.25 mm i.d.; 0.25 µm d f ; temperature: 150 – 185 ◦ C at 1 ◦ C/min; split injection 1/100; carrier gas nitrogen
at 18 psi (≈0.13 MPa); FID
Peaks: γ- (6 – 11) and δ-lactones (8 – 12)

Table 3. Retention times (n = 5) in initial runs, and predicted and experimental retention times at the optimum programming rate

Compound Symbol Initial runs Optimized program

No.Name 1 ◦ C/min, 12 ◦ C/min, Predicted, min Experimental,

min min min
1 Methyl butanoate C4 : 0 2.95 2.49 2.07 2.21
2 Methyl hexanoate C6 : 0 6.30 3.74 2.50 2.73
3 Methyl octadecanoate C8 : 0 14.65 5.38 3.01 3.32
4 Methyl decanoate C10 : 0 28.64 7.09 3.52 3.88
5 Methyl dodecanoate C12 : 0 45.02 8.69 4.00 4.41
6 Methyl phenylacetate I.S. ∗ 49.51 9.68 4.37 4.85
7 Methyl tetradecanoate C14 : 0 61.15 10.14 4.44 4.88
8 Methyl hexadecanoate C16 : 0 76.20 11.45 4.83 5.32
9 Methyl cis-9-hexadecanoate C16 : 1 cis 9 79.38 11.85 4.96 5.47
10 Methyl octadecanoate C18 : 0 90.08 12.65 5.19 5.72
11 Methyl cis-9-octadecanoate C18 : 1 cis 9 92.43 12.97 5.31 5.85
12 Methyl cis-9,12-octadecadienoate C18 : 2 97.23 13.47 5.48 6.04
13 Methyl cis-6,9,12-octadecatrienoate C18 : 3 γ 100.56 13.82 5.61 6.19
14 Methyl eicosanoate C20 : 0 102.95 13.75 5.55 6.11
15 Methyl cis-9,12,15-octadecatrienoate C18 : 3 α 102.95 14.03 5.68 6.27
16 Methyl docosanoate C22 : 0 114.64 14.77 5.92 6.49
17 Methyl cis-5,8,11,14-eicosatetraenoate C20 : 4 114.90 15.10 6.11 6.71
18 Methyl cis-4,7,10,13,16-eicosa-pentaenoate C20 : 5 120.20 15.64 6.39 6.89
19 Methyl tetracosanoate C24 : 0 126.08 15.72 6.34 6.97
20 Methyl cis-4,7,10,13,16,19-docosa-hexaenoate C22 : 6 133.60 16.83 7.15 7.64

∗ I.S. = Internal standard.

optimization is treated in detail in [27], [28].
Figure 16 shows the computer predicted (A) and
experimental (B) chromatograms for a complex
fatty acid methyl ester mixture (Table 3) at a
programmed temperature increase of 40 ◦ C/min
[29]. The column was 55 m in length, and a
remarkably good separation was achieved in
< 8 min. Without the aid of computer simula-
tion, such fast programming rates would never
have been considered for this separation.
4.2. Constant Pressure, Constant Flow,
and Pressure Programming
Flow programming offers advantages such as
reduced separation time, less column bleed,
and lower eluting temperature for labile com-
pounds but has not been widely used in gas
chromatography because temperature program-
ming is experimentally easier to perform. In
1990, electronic pressure control (EPC) [30]
was developed, which allows operation in the
18 Gas Chromatography
Figure 16. Predicted (A) and experimental (B) chromatograms for fatty acid methyl ester mixture with temperature-
programmed analysis at 40 ◦ C/min
constant-pressure, constant-flow, and pressure-
programming modes. Whether temperature pro-
gramming will be replaced by flow program-
ming is questionable, although the features of
EPC open new perspectives. Gases play a vi-
tal role in GC and are even more important in
CGC. The carrier gas is the force moving the so-
lutes through the column, and its velocity or flow
controls the chromatographic band broadening
and thus the efficiency. Keeping the velocity or
flow under control is a prerequisite for good GC
practice. Besides this, the carrier gas is often the
transport medium of solutes from injection de-
vices such as split, splitless, programmed-tem-
perature vaporizing inlets, purge and trap, ther-
mal desorption units, and pyrolysis units. Often
the flows required in the precolumn devices do
not correspond to the optimal carrier gas flows,
and compromises must be accepted (i.e., split
in purge and trap, long residence times of so-
lutes in a splitless liner). On the other hand,
optimization of total GC performance also re-
quires precise control of the flows of the detec-
tor gases responsible for detector sensitivity and
baseline stability. The quality of data generated
by the hyphenated spectroscopic methods (see
Section 6.4) also depends strongly on the stabil-
ity of the flows of reagent gases (e.g., in chemical
ionization mass spectroscopy and atomic emis-
sion detection). In the past, very little attention
was paid to the mode of operation of the dif-
ferent gases in a GC system, and all gas sup-
plies were more or less operated in the constant-
pressure mode. In the constant-flow mode, all
parts of a GC system run under optimum condi-
tions. EPC is likely to become a standard mode
of operation in the near future. The CGC appli-
cations with EPC published until now all show
improved chromatographic performance going
from reduced discrimination and large volume
introduction in splitless injection by a pressure
pulse shortening the residence time in the in-
let, to increased sensitivity by EPC control of
detector gases independently or in concert with
the carrier gas flow. These are just a few exam-
ples, and more features are detailed in [31]. Yet
more is to be expected because the possibilities
of EPC have not yet been fully evaluated and
exploited. A typical example can be found in
multidimensional CGC (see Section 8.1). One
of the reasons for slow acceptance of this ex-
tremely powerful technique is the necessary ad-
justment of the midpoint pressures, which can
require several days of fine tuning with con-
ventional pressure control devices. Flow control
at the midpoint should solve this shortcoming.

Nevertheless, EPC introduces a new era in good
laboratory practice (GLP) and good automated
laboratory practice (GALP). Analytical methods
can now be stored completely, providing exactly
the same flow characteristics of all gases and
tremendously enhancing repeatability and accu-
racy.
5. Sample Inlet Systems
5.1. General Considerations
“If the column is described as the heart of chro-
matography, then sample introduction may, with
some justification, be referred to as the Achilles
heel.” This statement [32] clearly illustrates that
sample introduction is of primary importance
in GC and especially capillary GC. The perfor-
mance of the sample introduction system is cru-
cial for overall chromatographic performance of
the complete system. Much progress has been
made in recent years, and the understanding
of injection phenomena has increased tremen-
dously. Because of the diversity of samples that
can be analyzed with modern GC (wide range of
component concentrations; from highly volatile
to less volatile components; different thermal
stabilities; etc.), several injection methods have
been developed. A final universal answer to sam-
ple introduction, however, has not been provided
yet, and whether such an answer can be provided
at all is questionable: “There does not now and
probably never will exist injector hardware or
methodology that is suitable for all samples, un-
der all conditions” [33]. “There is still no such
thing as a universal injection system and there
probably never will be” [34]. This does not mean
that precise and accurate results cannot be gen-
erated with the different injection systems that
have been optimized over the years. The possi-
bilities and the limitations of available systems,
however, must be known exactly. In combina-
tion with a sufficient knowledge of the composi-
tion of the sample to be analyzed, proper injector
choice will guarantee good results.
A qualitative and quantitative analysis means
that the chromatographically determined com-
position of the sample corresponds to its real
composition. Possible difficulties encountered
in obtaining such data have to be attributed to
the sampling technique, various column effects,
Gas Chromatography 19
or a combination of both. A sample introduction
system can be “discriminative”, meaning that
certain components are not introduced quanti-
tatively into the column. However, the column
itself can also act to discriminate (reversible
and/or irreversible adsorption), the degree of
which can, moreover, be injection dependent.
The characteristics of the column in use, there-
fore, must be well established before any con-
clusion can be drawn with regard to the sampling
system.
The basic prerequisite of a sampling system
for gas chromatography is that the sample must
be introduced into the column as a narrow band,
whose composition is identical to the original
composition of the sample. The width of the inlet
band must be such that its variance does not con-
tribute significantly, or contributes only slightly,
to the chromatographic broadening process. The
total measured variance σ total is the sum of all
contributions to the peak variance:
2 2 2 2
σtotal =σcolumn +σinjection +σextra (5.1)
With modern GC instrumentation, the extra
peak variance contribution (electrometer, data
system, recording) approaches zero. Because of
the occurrence of the squared variances in this
equation, the contribution of the initial band-
width to the total peak bandwidth is less dra-
matic than might be expected, at least for GC
on packed columns. For capillary columns, in-
jection bandwidths can be too large compared to
the chromatographic band broadening, and nar-
row initial bands have to be obtained by:
1) Introducing very small sample volumes (1 –
50 nL) into the column. A sample stream
splitting device (splitter) accomplishes this
task. The sample vapor, formed on injection
at elevated temperature, is split into two sam-
ple streams of different flow rates.
2) The entire sample is introduced into the col-
umn, but the broad initial band is imme-
diately focused into a narrow initial band
by sharpening mechanisms such as solvent,
thermal, or stationary-phase focusing. In
practice, these effects are used with great ad-
vantage to focus the solute bandwidths pro-
duced by splitless and on-column injection.
In subsequent sections, the most important
sample introduction systems will be discussed
20 Gas Chromatography
in some detail with emphasis on capillary in-
lets. Because of the much larger σ column in
packed columns, injection is less stringent. In-
lets are also divided into universal and selective
inlets. The aim of universal injection is intro-
duction of the complete sample into the column,
whereas selective injection means that only a
well-defined fraction enters the column.
Figure 17. Schematic of a packed column injector
a) Septum; b) Glass wool; c) Packing; d) Nut; e) Ferrule
5.2. Universal Inlets
5.2.1. Packed Column Inlets
Packed column inlets are simple to design and
use [35]. Injection is performed directly in the
column “on-column” (Fig. 17) or in an in-sert
placed before the head of the column. Different
inserts are used, depending on the type of packed
column (1/8 = 0.32 cm or 1/4 = 0.63 cm). Po-
lar and thermolabile compounds are most ef-
fectively analyzed by on-column injection on
a glass column. The injector zone is heated,
and upon manual or automated injection, usu-
ally with a microliter syringe, hot mobile-phase
gas carries the vaporized sample down to the
packing material. Packed column inlets are va-
porizing so they can cause sample degradation
and needle discrimination. This is discussed in
detail for split injection. Sampling valves are of-
ten used to sample gases or volatile liquids in
constant-flowing streams. The valve is substi-
tuted for the syringe and can be used both with
packed and with capillary columns. The con-
struction of GC valves is similar to HPLC valves.
5.2.2. Capillary Column Inlets
In the context of this contribution, it is impossi-
ble to treat every aspect of sample introduction
in capillary GC in depth. Full details on the dif-
ferent sampling methods can be found in [36],
[37]. A survey of sampling systems is also given
in [34], [38].
Figure 18. Schematic of a split injector
a) Septum; b) Needle valve; c) Vaporization chamber;
d) Capillary column

5.2.2.1. Split Injection
Split sampling was the first sample introduction
system developed for capillary GC [39]. The
conventional split injector is a flash vaporiza-
tion device. The liquid plug, introduced with a
syringe, is volatilized immediately, and a small
fraction enters the column, while the major por-
tion is vented to waste. This technique guaran-
tees narrow inlet bands. A schematic diagram of
a split injector is shown in Figure 18. Preheated
carrier gas enters the injector and the flow is
divided in two streams. One stream of carrier
gas flows upward and purges the septum (a).
The septum purge flow is controlled by a needle
valve (b). Septum purge flow rates are usually
between 3 and 5 mL/min. A high flow of carrier
gas enters the vaporization chamber (c), which is
a glass or quartz liner, where the vaporized sam-
ple is mixed with carrier gas. The mixed stream
is split at the column inlet, and only a small
fraction enters the column (d). A needle valve
controls the split ratio. Split ratios (i.e., col-
umn flow: inlet flow) range typically from 1 : 50
to 1 : 500 for conventional capillary columns
(0.22 – 0.32 mm i.d.). Lower split ratios can be
used in combination with focusing effects. For
columns with a high sample capacity such as
widebore or thick-film columns, low split ra-
tios (1 : 5 – 1 : 50) are common. In high-speed
capillary gas chromatography, applying 0.1 to
0.05 mm i.d. columns, split ratios can exceed
1 : 1000. In split injection, initial bandwidths are
only milliseconds. Because split injection is a
flash vaporization technique, sample discrimi-
nation is difficult to avoid. This is especially the
case if the sample contains components in differ-
ent concentrations and with different volatilities
and polarities. Sample discrimination in split in-
jection is caused by inlet-related parameters as
well as by operational parameters such as sy-
ringe handling. Inlet-related discrimination is
often referred to as nonlinearity of the splitter de-
vice. Linearity in this respect means that the split
ratio at the point of splitting is equal to the pre-
set split ratio and equal for all the components in
the sample. Linear splitting against varying sam-
ple components, be it in concentration, volatility,
or polarity, is impossible to achieve, even when
a sample is introduced in a nondiscriminative
manner into the vaporization chamber. Differ-
ent mechanisms can cause nonlinear splitting:
Gas Chromatography 21
different diffusion speed of the sample compo-
nents, incomplete evaporation, and fluctuating
split ratio. The different mechanisms and their
respective contribution are discussed in [36].
Nonlinearity can be minimized by complete va-
porization of the sample, followed by homoge-
neous mixing with the carrier gas before the sam-
ple enters the column. As evident as this may
seem, the sample introduced by split injection
often arrives at the point of splitting as a mixture
of vapor and a nonuniform mist of droplets. Two
approaches can be used to minimize this phe-
nomenon: (1) increased injection temperature
and (2) optimization of the inlet configuration
and glass liners. Different glass liners have been
proposed (i.e., empty tube, short glass-wool plug
in the splitting region, long and tight glass-wool
plug, packing with chromatographic support or
glass beads, deformation of cross section, Jen-
nings tube, etc.) with the aim of enhancing ef-
ficient heat transfer to the injected sample and
thoroughly mixing the vaporized sample. Still,
whereas such modifications demonstrate an im-
provement in linearity for some applications, the
same setup may give bad results for others. As
a general rule, packed liners should not be used
unless bad results have been obtained with an
open liner. When discussing nonlinearity, it was
taken for granted that sample introduction with
a syringe into the vaporization chamber occurs
without any alteration to the sample – in other
words, no discrimination is caused by the sy-
ringe introduction. However, most of the dis-
crimination problems encountered with vaporiz-
ing injectors are related to syringe needle effects.
Upon introducing the syringe needle through the
septum, volatiles immediately start to evaporate
inside the needle itself, which is heated by the
injector. Also after pushing down the plunger,
solvent and volatile solutes are evaporated more
readily than high-boiling solute material, which
partly remains on the needle wall. On removing
the needle from the injector body, the nonvolatile
components are taken out of the vaporization
chamber as well, resulting in a mass discrimina-
tion according to volatility. Different methods
of syringe manipulation have been studied (e.g.,
filled needle, cold needle, hot needle, solvent
flush, air flush, sandwich method) in combina-
tion with fast or slow injection. These different
procedures are not discussed here, but rather the
best method – “manual hot-needle, fast-sample
22 Gas Chromatography
introduction” – is described. This method guar-
antees minimal syringe discrimination, although
complete avoidance is impossible when dealing
with solutes having a large volatility difference.
In the hot-needle method, the sample is taken
into the syringe barrel, for example up to the 5-
µL mark when a 10-µL syringe is used, without
leaving an air plug between sample and plunger.
After insertion into the injection zone, the nee-
dle is allowed to heat up for 3 – 5 s. This time is
sufficient for the needle to be heated to the in-
jector temperature. The sample is then injected
by rapidly pushing the plunger down (fast injec-
tion), after which the needle is withdrawn from
the injector within 1 s. Syringe discrimination is
related to the warming up of the needle in the
vaporization chamber. Systems can be worked
out in which syringe discrimination is reduced
or avoided. The best technique is very fast in-
jection. A prerequisite here is automated cold-
needle sample introduction since all steps of the
injection sequence are identical for each injec-
tion. The objective of very fast injection is to
get the needle into the injection port, inject the
sample, and withdraw the needle so quickly that
it has no time to warm up, in this way avoid-
ing selective sample evaporation. Fast injection,
moreover, implies that the delivered volume of
sample equals the preset volume. The effect of
the needle dwell time in the injection port on
sample discrimination has been studied [40].
Dwell time is defined as the interval between
the needle tip piercing the septum on the way
in and reaching the same point on the way out.
Figure 19 shows a plot of CX : C20 area ratios
(X= 10 – 40) as a function of C-number for dif-
ferent dwell times, with hexane as the solvent.
Although these data have been obtained for di-
rect injection, they are also valid for split injec-
tion. A dwell time of 500 ms or less shows no no-
ticeable fractionation. Modern autosamplers in-
ject in 100 ms. The previous discussion indicates
that obtaining quantitative data by using a split
injector can be problematical, but not impossi-
ble. For samples in which the solutes do not dif-
fer too much in volatility, precision and accuracy
can be acceptable if the injection technique has
been optimized. Some summarizing guidelines
are given. In quantitative analysis, the standard
addition or the internal standard method is pre-
ferred for manual injections. External standard-
ization in which absolute peak areas are com-
pared can be applied only with fast automated
injection. Reproducibility will be enhanced by
not varying the injected volume, which typi-
cally should be 0.5 – 2 µL. Injector temperature
should be adapted to the problem at hand (i.e.,
close to the boiling point of the last eluting
compound). Excessively high injector temper-
atures should be avoided. The hot-needle, fast-
injection method is preferred for manual injec-
tion. The use of highly volatile solvents should
be avoided whenever possible. If an open liner
does not do the job, lose packing with deacti-
vated glass wool or glass beads can provide a
solution. However, adsorption and decomposi-
tion can occur. One of the main problems asso-
ciated with split injection is syringe handling.
The application of an autosampling system can
overcome this difficulty, enhancing both preci-
sion and repeatability. For several applications,
however, split injection will not give high quan-
titative accuracy.
Figure 19. Effect of needle dwell time on sample discrim-
ination
5.2.2.2. Splitless Injection
In splitless injection a conventional split injec-
tor is operated in a nonsplitting mode by closing
the split valve during injection. The sample is
flash vaporized in the vaporizing chamber from
which the sample vapors are carried to the col-
umn by the flow of the mobile phase. Since this
transfer takes several tens of seconds, broad ini-
tial bandwidths would be anticipated. However,
through optimal use of focusing effects, such as
solvent, thermal, and stationary-phase focusing,
initial peak broadening can be suppressed. The

main feature of splitless injection lies in the fact
that the total injected sample is introduced in the
column, thus resulting in much higher sensitiv-
ity compared to split injection. For a long time,
splitless injection was the only sample introduc-
tion technique in capillary GC for trace analy-
sis. The pneumatic configuration is similar to the
classical split injector (see Fig. 18). The septum
is purged continuously (flow rate 2 mL/min) to
maintain the system free of contamination, while
a flow of 20 – 50 mL/min passes the split outlet.
Prior to injection, a solenoid valve is activated,
so that the splitline is closed off while the sep-
tum purge is maintained. After waiting a suf-
ficient time for the solvent – solute vapor to be
transferred onto the column (i.e., 30 – 80 s), the
solenoid valve is deactivated. Residual vapors in
the vaporizing chamber are vented to waste via
the split line. For this reason, in splitless injec-
tion the split line is often referred to as the purge
line. The time interval between the point of injec-
tion and the activation of the split (purge) line is a
function of the characteristics of solvent and so-
lutes, the volume of the vaporizing chamber, the
sample size, the injection speed, and the carrier
gas velocity. The sample transfer from the vapor-
izing chamber into the column is a slow process.
Solvent vapors especially tend to remain in the
inlet for a long time. Purging the insert after in-
jection removes the last traces of vapor from the
vaporizing chamber. An important aspect in the
design of a splitless injector is the dimension of
the vaporizing chamber. Long and narrow inserts
are preferred to obtain minimal sample dilution.
Internal volumes vary between 0.5 and 1 mL.
The column is installed 0.5 cm in the insert, and
syringes with long needles are used, creating a
distance of 1 – 1.5 cm between the needle tip and
the column inlet. Overfilling of the vaporizing
chamber is suppressed, and fast sample transfer
is achieved. If sample volumes larger than 2 µL
are injected, a widebore liner should be used.
Because of the relatively long residence time of
the solutes in the vaporizing chamber, lower in-
jection temperatures can be used compared to
split injection. This can be helpful in minimiz-
ing sample degradation. For the same reason,
the use of packed inserts should be avoided in
splitless injection. An illustration of the effect of
glass or fused silica wool in the liner is presented
in Figure 20. The organochloropesticide endrin
(peak 1) tends to decompose into endrin alde-
Gas Chromatography 23
hyde (peak 2) and endrin ketone (peak 3) when
active sites are present in the liner. The first chro-
matogram shows that with an empty liner, 92 %
of the endrin is detected, compared to cool on-
column injection, which provides 100 % elution.
Filling the liner with a 1- cm plug of glass wool
or fused silica wool results in the elution of
only 83 % and 48 % endrin, respectively. Tak-
ing into account the fact that endrin is not the
most thermolabile compound, what will happen
if polar compounds (i.e., carbamates, barbitu-
rates, etc.) are injected with filled liners can eas-
ily be imagined. Electronic pressure control was
introduced to reduce the residence time of the
solutes in the liner. With EPC, the carrier gas
pressure or flow can be programmed. During in-
jection a very high flow rate is applied, which
speeds up the transfer liner – column. After in-
jection, the flow is reset to the optimal value
for the column in use [41]. Syringe discrimina-
tion, which is one of the largest sources of error
when applying split injection, also occurs for
splitless injection because both are vaporizing
inlets. The performance of a splitless injector for
a particular application depends on the optimiza-
tion of experimental variables, the most impor-
tant of which are sample size, injection speed,
purge time, injection temperature, initial col-
umn temperature, carrier gas selection, and flow
rate. General guidelines cannot be advanced, and
some of the variables can be only tuned by trial
and error. Whatever the application, however, re-
focusing of the solutes in the inlet section of the
capillary column is necessary. In splitless injec-
tion, the initial bandwidths are broadened by two
mechanisms: band broadening in time and band
broadening in space. Band broadening in time is
caused by the slow transfer from the vaporizing
chamber to the column inlet section, which takes
several tens of seconds. Upon their arrival in the
column, the solutes spread over a certain column
length, mainly by flooding of the sample liquid,
thus causing band broadening in space. The fun-
damental difference between band broadening in
time and band broadening in space is that, in the
first case, solutes are spread equally with respect
to gas chromatographic retention time, whereas
in the second case, solutes are spread equally
with respect to column length. Both phenom-
ena cause distorted elution profiles if the solutes
are not refocused before starting the chromato-
graphic distribution process.
24 Gas Chromatography
Figure 20. Decomposition of endrin on different splitless liners
A) Empty liner; B) 1-cm plug of glass wool; C) 1-cm plug of fused silica wool
Solvent Focusing, Thermal Focusing, and
Stationary-Phase Focusing. Splitless injection
most often is combined with column tempera-
ture programming, starting with an oven tem-
perature 25 – 30 ◦ C below the boiling point of
the solvent. Upon condensation of solvent and
solutes, the droplet formed becomes too thick to
be stable. The carrier gas pushes the plug fur-
ther into the column, creating a “flooded zone”
(Fig. 21). The solutes now are spread over the
full length of the flooded zone, thus creating a
solute bandwidth that equals the length of the
flooded zone. For 1-µL injections, the length
of the flooded zone roughly is 20 cm, provided
the stationary phase is perfectly wettable by
the solvent [i.e., isooctane solutions on apolar
methylsilicone phases, ethyl acetate solutions
on poly(ethylene glycol) phases]. On conven-
tional capillary columns, 25 – 30 m in length,
i.d. 0.32 mm, band broadening will hardly be
observed for sample volumes of 1 µL. Only for
sample sizes larger than 2 – 3 µL will peak de-
formation be noted. On the other hand, for polar
solvents on apolar stationary phases, the length
of the flooded zone can be as large as 1 m, result-
ing in distorted peaks. Stationary phase focusing
then becomes necessary. After creation of the
flooded zone, the temperature is increased and
the solvent starts to evaporate from the rear of
the flooded zone (Fig. 22). Highly volatile so-
lutes evaporate as well and the last traces of
solvent act as a barrier since the residual sol-
vent behaves as a thick stationary-phase film for
those solutes. High volatiles are thus focused
by the solvent effect. The low-volatility solutes
are cold trapped since the column temperature
is still too low to evaporate them. They are ther-
mally focused over the length of the flooded
zone. When the temperature is high enough to
evaporate the low-volatility solutes, they start
the chromatographic process at different points.
If the flooded zone is homogeneous and short,
peak distortion is hardly observed, but when
the flooded zone is inhomogeneous and long,
which is the case when polar solvents are in-
jected on apolar capillary columns, broad dis-
torted peaks are detected. The only reason for
this is that the chromatographic process starts
with the solutes distributed over the length of
the flooded zone. This can be avoided by re-
moving the stationary phase over the length of
the flooded zone or, in other words, by creating
a retention gap. Band broadening in space can
thus be suppressed by stationary-phase focus-
ing via a retention gap (Fig. 23). A retention gap
is a definite length of the separation system that
is uncoated. All solutes that are spread over the
flooded zone are carried with no retention onto
the stationary phase where they are retained. In
practice, a retention gap is a separate piece of
deactivated fused silica, connected to the ana-
lytical column through a coupling device such
as a press fit connector. The length of the reten-
tion gap is a function of the length of the flooded
zone, and depends on the sample volume and
the nature of the solvent in use. Typical lengths
are 0.5 – 1 m for injections of 1 to 2 µL. Longer
lengths, however, do not harm the separation,
and pieces of 3 m are standard and commercially
available. Band broadening in space and the use
of a retention gap are also required for cool on-
column injection (see Section 5.2.2.3). In recent
years, splitless injection has been overshadowed
by cool on-column injection. Without any doubt,
 Gas Chromatography 25

the most accurate and precise data are now pro-

vided with on-column injection. Notwithstand-
ing this, splitless injection is still used for many
routine determinations (i.e., in environmental
analysis, pesticide monitoring, drug screening,
etc.). In these fields, sample preparation is of
primary concern, and cleaning up a sample to
such an extent that it is accessible to on- column
injection is not always possible or economically
justifiable. Traces of nonvolatile or high-boiling
components often remain in the sample. Split-
less injection is an easy solution to such prob-
lems. The “dirty” components remain mainly in
the vaporizing inlet, which is easily accessible Figure 22. The solvent and thermal focusing effect
for cleaning. An illustration of the determination o = High-volatile solute; • = Low-volatile solute
of polychlorinated biphenyls (PCBs) in waste
oil via splitless injection is shown in Figure 24.
5 µL of an isooctane solution of the PCBs ex-
tracted from waste oil, was injected in the split-
less mode on an apolar column equipped with
a retention gap of 5 m. A pressure pulse was
applied to minimize the residence time of the
solutes in the liner [42]. Without a retention gap
the flooded zone would have been too large to
guarantee good peak shapes. When properly per-
formed, reproducibility in splitless injection can
be as high as 1 – 2 % relative standard deviation
(RSD). Standard addition or internal standard
quantitation is the method of choice for manual
injection. The external standard method can be Figure 23. Stationary-phase focusing and the principle of
adapted for automated splitless injection. Many a retention gap
capillary GC applications need the best attain- • = Low-volatile solute
able precision and accuracy. Cool on- column in-
jection (see Section 5.2.2.4) then is the method
of choice. 5.2.2.3. Direct Injection
The nomenclature of different injection
techiques has been created as new develop-
ments occur. This often causes confusion with
regard to the interpretation of some terms, which
do not always stand for what they really mean.
Direct injection is an example of such an ex-
pression, often confused or even identified with
on-column injection. The understanding of the
terminology given in this article, based on the
chronological order in which techniques were
developed, is as follows: Direct injection is a
flash vaporizing injection method. The inlet
system is heated separately and independently
from the column oven, and evaporation occurs
Figure 21. Creation of the flooded zone in the inlet. This inlet can be a glass liner (out-
o = High-volatile solute; • = Low-volatile solute
column evaporation) or a part of the column
26 Gas Chromatography
Figure 24. Optimized splitless injection of a PCB sample
Column: 25 m L×0.25 mm i.d.; 0.25 µm d f MeSi; retention gap: 5 m L×0.25 mm i.d.; temperature: 150-280 ◦ C at 5 ◦ C/min;
splitless injection with pressure pulse; carrier gas hydrogen; FID
(in-column evaporation). Different direct injec-
tion devices are shown in Figure 25. On-column
injection is a “cold” injection technique. The
sample is injected as a liquid, directly on the
column. During injection, the injection zone is
cooled to avoid needle discrimination. Injection
peak broadening is caused only by band broad-
ening in space. The solutes are focused in the
inlet section of the column, from where evapo-
ration gradually starts as the oven temperature
is raised. Whereas on-column injection can be
applied for all conventional capillary columns
(i.d. 0.25, 0.32, 0.53 mm), direct injection is
restricted to widebore or megabore columns.
Direct injection into widebore columns was
described in 1959 [43]. At that time, column effi-
ciency was all important. Through the introduc-
tion of widebore fused-silica capillary columns
with i.d.’s of 0.53 mm, the interest in direct sam-
pling has been renewed. Injection on a 0.53-
mm i.d. FSOT column, operated in the high-
resolution (flow rates 1 – 3 mL/min) or the low-
resolution (flow rates 8 – 12 mL/min) mode, as a
packed column alternative, is said to be as easy
as installing a simple glass liner in the packed
column inlet and connecting the column to it.
This view is slightly oversimplified since the di-
rect injection technique is based on the evapora-
tion of the sample at elevated injection temper-
ature, all previous statements about syringe dis-
crimination and band broadening effects remain
valid. Direct injection must definitely be opti-
mized according to the problem at hand. Some
experience-based guidelines on direct injection
into widebore columns are advanced. However,
when widebore capillary columns are used in
the high-resolution mode, they should be con-
nected to conventional capillary injectors (split,
splitless, on- column, programmed temperature
vaporization). For direct injection on widebore
columns operated at high flow rates, the sam-
ple size should be kept as small as possible, and
the sample should preferably be injected with an
autosampler. For manual injections, the fast hot-
needle injection technique is preferred to min-
imize syringe discrimination. To avoid sample
losses due to overfilling the insert with sample
vapors, the point of injection should be close to
the column entrance. Long and narrow inserts
are preferred to obtain minimum sample dilu-

tion (band broadening in time). Band broadening
should be compensated by refocusing the solutes
in the inlet section of the column. The principle
of the solvent effect and of thermal focusing have
been discussed in Section 5.2.2.2. Injections of
microliter volumes at oven temperatures (far)
above the boiling point of the solvent should
be avoided, unless the sample is known to con-
tain heavy compounds only, which will be re-
focused by cold trapping at the chosen column
temperature. Figure 26 shows the analysis of the
oxygenated fraction of hop oil dissolved in di-
chloromethane on a narrowbore column with
split injection (Fig. 26 A) and on a widebore col-
umn with direct injection (Fig. 26 B) [44]. Both
columns (25 m×0.25 mm and 50 m× 0.50 mm)
offer the same efficiency. Peak broadening did
not occur on the widebore column with direct
injection, for which only 0.2 µL was injected.
Figure 25. Different injection devices for direct injection
a) Open liner; b) Open liner with conical contraction;
c) Direct on-column liner; d) Open liner with expansion vol-
ume
5.2.2.4. Cool On-Column Injection
Syringe on- column injection with small-
diameter capillary columns was first described
in 1978 [45], [46]. Special on- column devices
Gas Chromatography 27
(a micro and a macro version) were introduced
in 1977 by Schomburg et al. [47], but the tech-
nical requirements were stringent and the de-
vices lacked practical flexibility. Since this pio-
neering work, all instrument manufacturers have
introduced cool on-column injectors. As an ex-
ample, the cool on- column injector developed
by Hewlett – Packard is shown in Figure 27. It
can be used for manual and automated injec-
tion. The injector has a low thermal mass, which
facilitates cooling. A key part of the injector
for manual operation is the duck bill valve (b).
The duck bill valve, made out of a soft elas-
tomer, is a passive element in that it has no
moving parts. It consists simply of two surfaces
pressed together by the column inlet pressure.
During injection, the syringe needle slips bet-
ween the two surfaces to maintain the seal. For
automated cool on-column injection, the sys-
tem is modified with a disk septum (h). Today,
cool on-column injection systems can be oper-
ated in the constant-pressure, constant-flow, or
pressure-programmed mode. These features al-
low reduction of analysis time and elution of
high molar mass compounds. The advent of cool
on-column injection has extended the range of
applicability of capillary GC to many classes of
compounds that heretofore were difficult if not
impossible to analyze. The technique of intro-
ducing the sample directly on the column with-
out prior vaporization offers many advantages,
such as elimination of sample discrimination and
sample alteration, high analytical precision, and
data operator independence. As with all other
sampling techniques, the operational parameters
strongly affect the chromatographic data. Pa-
rameters such as initial column temperature, sol-
vent nature, injection rate, injected volume, and
boiling point range of the sample components
are interrelated. Once again, all aspects cannot
be treated in detail in this article. On-column
Injection in Capillary GC by K. Grob contains
590 pages [37] ! The characteristics of the tech-
nique are highlighted here, and some important
aspects for daily practical use are discussed. For
sample sizes of the order of 0.5 –2 µL, injection
should be performed as quickly as possible, with
the column oven temperature below or equal to
the boiling point of the solvent. The oven tem-
perature in on-column injection may be higher
than in splitless injection. In splitless injection,
the solvent has to recondense; whereas in on-
28 Gas Chromatography

Figure 26. Analysis of the oxygenated fraction of hop essential oil on a conventional and a widebore capillary column
A) Column: 25 m L×0.25 mm i.d.; 0.25 µm d f high-M r poly(ethylene glycol); temperature: 70 – 190 ◦ C at 2 ◦ C/min; split
injection 1/20; carrier gas hydrogen; FID; B) Column: 50 m L×0.5 mm i.d.; 0.25 µm d f high-M r poly(ethylene glycol);
temperature: 70 – 190 ◦ C at 2 ◦ C/min; direct injection; carrier gas hydrogen; FID

column injection, the liquid is introduced di-
rectly into the column. As in splitless injection,
the length of the flooded zone must be reduced
because solutes are distributed over its entire dis-
tance. The width of the initial band equals the
length of the flooded zone, i.e., band broaden-
ing in space (band broadening in time does not
occur in on- column injection). The length of the
flooded zone is a function of the column diame-
ter, the volume injected, the actual inlet temper-
ature, the stationary-phase thickness, and, most
important, the affinity of the solvent for the sta-
tionary phase. For perfect wettability (i.e., apolar
solvents on apolar silicone phases), the length of
the flooded zone is about 20 cm per microliter in-
jected. This length easily increases by a factor of
five or ten if the wettability is poor, such as for
methanol injections on apolar silicone phases. If
the solutes are not refocused, band broadening
in space makes qualitative and quantitative anal-
ysis impossible if large sample volumes are in-
jected or if the solvent does not properly wet the
stationary phase. The latter phenomenon is il-
lustrated in Figure 28 with the analysis of a frac-
tion collected from a step-elution HPLC analysis
of the essential oil of Valeriana celtica L., with
hexane and methanol. The fraction of the polar
compounds was contained in 1 mL of hexane and
6 mL of methanol in a two-phase system. Both
phases were injected on-column (1 µL) onto a
20 m×0.3 mm i.d. methylsilicone column with
a film thickness of 0.3 µm. Figure 28 A shows
the chromatogram of the hexane layer and Fig-
ure 28 B that of the methanol layer. Methanol
causes peak splitting, whereas hexane does not
[48] . The poor wettability (polar – apolar) in the
case of methanol results in a long, nonhomo-
geneous flooded zone. This artifact can be by-
passed via a retention gap (see Section 5.2.2.2).
On-column injection provides the most accurate
and precise results because syringe discrimina-
tion, which is one of the main sources of error
in the quantitative analysis of samples cover-
ing a wide range of molar masses, is completely
avoided. Moreover, inlet-related discrimination
does not occur either, because the liquid is in-
troduced directly onto the column. The auto-
mated on- column analysis of free fatty acids
from acetic to decanoic acid is shown in Fig-
ure 29. Relative standard deviations on absolute
peak areas are < 1 % and on relative peak areas
< 0.4 %, for 20 injections (n = 20). The analysis
Gas Chromatography 29
Figure 27. Schematic of a cool on-column injector
a) Cool tower, needle guide; b) Duck bill valve (isolation
valve); c) Spring; d) Insert; e) Cryogenic cooling (optional);
f ) Heater block; g) Column; h) Septum
of polymer additives covering a broad range of
functionalities and molecular masses is shown in
Figure 30 [49]. To elute Irganox 1010 (M r 1176)
in a reasonable time, cool on-column injection
was performed in the constant-flow mode. Both
the external standard and the internal standard
method can be applied for quantitation. Current
literature data contain overwhelming evidence
for the superior features of cool on- column in-
jection in quantitative work. A second important
feature of cold on- column injection is the elim-
ination of sample alterations. Thermally labile
components are not exposed to thermal stress:
they begin the chromatographic process at rela-
tively low temperature. Decomposition and rear-
rangement reactions are nearly completely elim-
inated. This feature allows analyses that hereto-
fore were impossible with gas chromatography.
Figure 31 shows the analysis of some retinoids
[50]. Quantitative analysis in plasma samples
was possible only with cool on- colum injection.
The only disadvantage of cool on-column injec-
tion is that since the sample is introduced di-
rectly onto the column, relatively “clean” sam-
ples have to be prepared. Nonvolatile and less
volatile material collects at the head of the col-
umn. The presence of this material causes a loss
of separation efficiency or introduces adsorptive
sites in the column inlet. Proper sample cleanup
is thus very important. The use of a precolumn
30 Gas Chromatography
Figure 28. Illustration of peak splitting in cool on-column injection
A) Hexane as solvent; B) Methanol as solvent
Figure 29. Analysis of free fatty acids on a widebore cap-
illary column
Column: 10 m L×0.53 mm i.d.; 0.25 µm d f FFAP; tem-
perature: 60 – 100 ◦ C balistically, to 140 ◦ C at 2 ◦ C/min;
cool on-column injection; carrier gas hydrogen 4 mL/min;
FIDPeaks: (1) acetic acid, (2) propionic acid, (3) isobutyric
acid, (4) butyric acid, (5) isovaleric acid, (6) valeric acid,
(7) isocaproic acid, (8) caproic acid, (9) heptanoic acid,
(10) octanoic acid, (11) nonanoic acid, (12) decanoic acid
of 3 m, which at the same time acts as a retention
gap, is therefore recommended. When the chro-
matographic performance decreases, 5 to 10 cm
of the inlet section of the pre-column is cut off,
restoring the original performance of the system.
5.2.2.5. Programmed-Temperature Injection
In 1979, Vogt and coworkers [51] described an
injection method for the introduction of sam-
ple volumes up to 250 µL. The sample was in-
troduced slowly into a cold glass insert packed
with glass wool. The low-boiling solvent was
evaporated continuously and vented through the
split exit. The solutes, which remained in the
inlet, were transferred to the capillary column
by rapidly heating (30 ◦ C/min) the inlet. Dur-
ing this transfer, the split line was closed (split-
less injection). Based on this idea, the groups
of Schomburg [52] and Poy [53] almost si-
multaneously developed programmed-tempera-
ture injection. Their aim, however, was not the
injection of large sample volumes but rather
the elimination of syringe needle discrimina-
tion, which at that time was the subject of inter-
est. Different programmed-temperature vapor-
ization (PTV) injection devices are now com-
mercially available, offering a broad range of
possibilities (i.e., hot or cold split injection, hot
or cold splitless injection, cool on- column in-
jection, direct injection, etc.). Through these
possibilities, together with features such as the
injection of large sample volumes, concentra-
tion by multiple injection, solvent venting, etc.,
PTV injection is claimed to be the most uni-
versal sample introduction system. It is, how-
 Gas Chromatography 31

Figure 30. Analysis of polymer additives by high-temperature capillary GC

Column: 25 m L×0.32 mm i.d.; 0.17 µm d f MeSi; temperature: 80 – 380 ◦ C at 10 ◦ C/min; cool on-column injection; carrier
gas hydrogen 50 kPa constant flow; FID
Peaks: (1) butyl-4-methoxyphenol, (2) diethyl phthalate, (3) dibutyl phthalate, (4) Tinuvin P, (5) triphenyl phosphate, (6) dicy-
clohexyl phthalate, (7) dioctyl phthalate, (8) Tinuvin 327, (9) benzophenone UV, (10) erucamide, (11) Tinuvin 770,
(12) Irgaphos 168, (13) Irganox 1076, (14) Tinuvin 144, (15) Irganox 245, (16) Irganox 259, (17) Irganox 1035,
(18) Irganox 565, (19) crodamide, (20) Irganox 1098, (21) Irganox 3114, (22) Irganox 1330, (23) Irganox PS 802,
(24) Irganox 1010

ever, not the best choice for all applications. The
upper part of a PTV inlet resembles a classi-
cal split – splitless device, including carrier gas
inlet and septum flush. The sample is injected
into a glass liner with a low thermal mass while
the injector body is cold. After withdrawal of
the syringe needle, the vaporizing tube is heated
rapidly to volatilize the solvent and the solutes.
The heat can be provided electrically or by
means of preheated compressed air. Depend-
ing on its construction, heating of the device
can be performed ballistically or linearly at se-
lected rates (for example 2 – 12 ◦ C/s) and even to
consecutive temperature levels. These facilities
allow optimization of conditions for the analy-
sis of thermally labile compounds, operating in
the solvent vent mode when working with spe-
cific detection such as electron capture detec-
tion (ECD) or mass spectrometry, concentration
through multiple injection, etc. Split or splitless
injection can be achieved through regulation of
the split valve. During or after the chromato-
graphic run, the vaporizing chamber is cooled
by air or carbon dioxide, in preparation for the
next injection. In an interesting mode of opera-
tion (i.e., solvent elimination injection), the sam-
ple is introduced into the cold injector with the
split valve open. Conditions are selected such
that only the solvent evaporates while the so-
lutes of interest remain in the liner. The appli-
cability of this technique is, therefore, restricted
to the analysis of relatively high-boiling com-
pounds. In this way, large sample volumes can
be introduced to enrich traces. The principle has
been applied to detect dioxins and furans down
to the 100-fg/µL level with capillary GC – low-
resolution mass spectroscopy [54].
5.3. Selective Inlets
A number of selective inlets are available in GC.
Best known are static and dynamic head space
(HS) injection (selectivity based on vapor pres-
sure), purge and trap (PT) samplers (selectivity
based on solubility of the solutes in water), ther-
mal desorption (TD) units (selectivity based on
characteristics of the adsorbent), and pyrolysis
units (selectivity based on the pyrolysis or crack-
ing temperature). These inlets are discussed in
Sections 5.3.1 – 5.3.4. More sophisticated sys-
tems, which can also be considered as sample in-
troduction systems, such as solid-phase extrac-
32 Gas Chromatography

Figure 31. Illustration of the application of cool on-column injection to the analysis of thermolabile compounds
Column: 12.5 m L×0.25 mm i.d.; 0.25 µm d f CPSi; temperature: 60 – 190 ◦ C at 17 ◦ C/min, to 220 ◦ C at 6 ◦ C/min and to
235 ◦ C at 1.5 ◦ C/min; cool on-column injection; carrier gas hydrogen; FIDPeaks: (1) trans-acitretin methyl ester, (2) cis-
acitretin methyl ester, (3) cis-acitretin propyl ester

tion (SPE; selectivity based on the polarity of
both adsorbent and desorbing liquid), supercrit-
ical fluid extraction (SFE; selectivity based on
the solubility in the supercritical medium, the
variables being density, temperature, pressure,
and polarity), multidimensional capillary GC
(MDCGC), the combinations of capillary GC
with liquid chromatography (HPLC – CGC) or
with supercritical fluid chromatography (SFC –
CGC) allowing preseparation according to mo-
lar mass (size-exclusion chromatography, SEC),
functionality (normal phase LC), hydrophobic-
ity (reversed phase LC), or solubility (SFC) are
treated in Chapter 8. In addition, on-line sam-
ple preparation units became available in 1993,
providing functions such as dispensing (addi-
tion of reagents or internal standards), diluting
(concentration adjustments and multipoint cali-
bration standards), heating (derivatization, solu-
bilization), evaporating (solvent exchange, con-
centration), solid-phase extraction, and filtering.
5.3.1. Static and Dynamic Head Space
Analysis
Head space analysis is used to analyze volatiles
in samples for which the matrix is of no in-
terest (i.e., water, soil, polymers, etc.). Typical
applications include monitoring of volatiles in
soil and water (environmental); determination of
 Gas Chromatography 33

monomers in polymers, aromas in food and bev- amounts of volatile aromatics, trihalomethanes,
erages, residual solvents in drugs (pharmaceu- etc.
ticals), etc. Different head space autosamplers
are commercially available, and they are based
on the principle of static or dynamic head space.
The difference between these modes is depicted
in Figure 32. In static head space (Fig. 32 A), the
sample (soil, water, solid) is transferred in a head
space vial that is sealed and placed in a thermo-
stat to drive the desirable components into the
head space for sampling. Via a gas-tight syringe
(a) or a sample loop of a gas sampling valve, an
aliquot of the vapor phase is introduced in the GC
system, which can be equipped with a packed or
a capillary column. Because of the much lower
sample loadability of a capillary column, split in-
jection is usually applied in this case. Static head
space implies that the sample is taken from one
phase equilibrium. To increase detectability, dy-
namic head space analysis has been developed.
The phase equilibrium is continuously displaced
by driving the head space out of the vial via an
inert gas. The solutes are focused by cold trap
(e) or an adsorbent such as Tenax and after en-
richment the trap is heated and the solutes are
Figure 32. Principle of static (A) and dynamic head space
introduced into the GC system. Whereas static (B)
head space is applied to analyze ppm amounts a) Syringe;b) Head-space bottle; c) Thermostat;d) Injector;
(1 part in 106 ), dynamic headspace allows de- e) Cold trap; f ) Solid-phase extraction
termination of ppb amounds (1 part in 109 ) of
volatiles. Sample pretreatment can often help to
increase sensitivity and enhance reproducibility. 5.3.3. Thermal Desorption Units
The best-known methods are salting out of wa-
ter samples with sodium sulfate, adding water Thermal desorption is the method of choice to
to solid samples, and adjusting the pH to drive monitor air pollution. A known amount of air is
organic acids or bases into the head space. drawn through an adsorbent tube filled with ac-
tivated carbon, Tenax, silicagel, or mixtures of
these. Analytes of interest are trapped and con-
5.3.2. Purge and Trap Systems centrated on the adsorbent. The adsorbent tube
is sealed and transported to the laboratory where
Purge and trap samplers have been developed for it is installed in the thermal desorption unit. An
analysis of apolar and medium-polarity pollu- example of a thermal desorption unit is shown in
tants in water samples. The commercially avail- Figure 33. After the adsorbent tube is placed in
able systems are all based on the same prin- the desorption module, the carrier gas is directed
ciple. Helium is purged through the sample over the adsorbent, which is heated from room
placed in a sealed system, and the volatiles are temperature to 250 – 300 ◦ C. Since thermal des-
swept continuously through an adsorbent trap orption is a slow process, the solutes are focused
where they are concentrated. After a selected by cold trapping on a fused silica trap. The cryo-
time (10 – 20 min), purging is stopped, the car- genic trap is then heated rapidly to transfer the
rier gas is directed through the trap via a six-way sample to the column. The method works well
valve, and the trap is heated rapidly to desorb for apolar and medium-polarity components in
the solutes. The method has proven to be highly air. Highly polar solutes are very hard to desorb,
accurate for environmental monitoring of ppb and other sampling methods must be selected.
34 Gas Chromatography
Figure 33. Schematic of a thermal desorption unit
a) Adsorbent tube; b) Heating device; c) FSOT trap;
d) Cooling; e) Heating
5.3.4. Pyrolysis Gas Chromatography
Pyrolysis involves the thermal cleavage (crack-
ing) of large molecules, which are not amenable
to GC, into small volatile fragments. Pyroly-
sis GC is an excellent technique for identifying
polymers and microorganisms because the pyro-
lysis profiles are very typical fingerprints. Most
important in this respect is the pyrolysis temper-
ature, typically between 400 and 1000 ◦ C. The
higher the temperature, the greater is the degree
of fragmentation. Several types of analytical py-
rolyzers are available. The most common types
are the platinum resistively heated and the Curie
point pyrolyzers. Figure 34 shows an example of
a resistively heated pyrolyzer. The pyroprobe (c)
consists of an injector cap (a), a quartz tube (d),
and a platinum wire (f ). The sample is placed in
the quartz tube, and the pyroprobe is introduced
in the injection port of the GC. The carrier gas
enters the system, and after equilibration, the
platinum wire is heated to a preselected temper-
ature. The material decomposes and the volatiles
are analyzed.
Figure 34. Principle of pyrolysis GC
a) Injector cap; b) Septum; c) Pyroprobe; d) Quartz tube;
e) Glass wool; f ) Platinum wire; g) Inlet liner
6. Detectors
Detectors in gas chromatography sense the pres-
ence of analytes in the carrier gas and convert
this information in an electrical signal, which
is recorded. Numerous detection devices have
been developed in GC [55]; here, only the cur-
rently most common detectors are dealt with. An
excellent book describing detectors for capillary
chromatography has been published [56].
6.1. Classification
GC detectors are classified mainly on the ba-
sis of response or of detector selectivity. Detec-
tors whose response is proportional to the con-
centration of a sample component in the mobile
phase (g/mL) are called concentration-sensitive
detectors, whereas detectors whose response is
proportional to the amount of sample compo-
nent reaching the detector in unit time (g/s)
are called mass-flow detectors. Universal detec-
tors respond to every component in the mobile
phase; selective detectors respond only to a re-
lated group of substances; and specific detec-
tors respond to a single sample component or
to a limited number of components with similar
chemical characteristics. The differentiation of

selective versus specific is confusing, and there-
fore in this article, selective is used for both to
distinguish them from universal. Another classi-
fication is destructive versus nondestructive de-
tectors. Any detector can be coupled in series
with a nondestructive detector. The most impor-
tant characteristics for practical work are sensi-
tivity, dynamic range, linear range, detector re-
sponse factors, and selectivity.
Figure 35. Dynamic range of a GC detector
a) Minimum detectability; b) Upper limit of linearity
Sensitivity is the signal output per unit con-
centration or unit mass of a substance in the
mobile phase and is best expressed by the min-
imum detectable quantity, which is defined as
the concentration or the amount of analyte for
which the peak height is four times the intrin-
sic noise height of the detector (signal-to-noise
ratio S/N = 4). The dynamic range of a detector
is that range of concentration or quantity over
which an incremental change produces an in-
cremental change in detector signal. Figure 35
represents a plot used for the determination of
the dynamic range of a detector. That part of the
curve for which the response increases propor-
tionally with increased concentration or quantity
is called the linear range. For quantitation, work
in the linear range is preferable, it is expressed
numerically as the ratio of the upper limit of lin-
earity (b) to the minimum detectability (a), both
measured for the same substance. The detector
response factor f i is a relative term expressing
the sensitivity of a detector to a given compound
Gas Chromatography 35
i, relative to its sensitivity to a standard com-
pound:
fi =fst (Ai /Ast ) (6.1)
where Ai and Ast are the respective peak areas
and f st is the detector response factor for the
standard; f st is usually assigned a value of 1.000.
Detector selectivity is the ratio of the signal
obtained for a compound to which the detector
has special selectivity versus the signal obtained
for a compound to which the detector is not par-
ticularly sensitive. Both signals must be mea-
sured for equal amounts. A compilation of selec-
tivity, minimum detectability, and linear range
of the most common GC detectors is given in
Table 4.
6.2. Universal Detectors
6.2.1. Flame Ionization Detector
The flame ionization detector (FID) is the most
widely used GC detector. Its operation is sim-
ple, sensitivity is of the order of 10 pg carbon
per second with a linear range of 107 , the re-
sponse is fast, and detector stability is excel-
lent. The carrier gas is mixed with hydrogen, and
this mixture is combusted in air at the exit of a
flame jet. Ions are formed that are collected at
an electrode producing a current that is propor-
tional to the amount of sample compound in the
flame. Analytes such as permanent gases, nitro-
gen oxides, sulfur oxides, carbon oxides, carbon
disulfide, water, formic acid, formaldehyde, etc.,
do not provide a significant FID response. The
flows of carrier and combustion gas should be set
properly for optimal FID operation. Typical flow
rates are 1 : 1 : 12 (30 : 30 : 360 mL/min), respec-
tively, for nitrogen as carrier gas, and the com-
bustion gases hydrogen and air. If hydrogen is
applied as carrier gas in packed column GC, the
hydrogen combustion gas is replaced by nitro-
gen. For capillary GC where the carrier gas flows
are much lower (e.g., 1 – 3 mL/min), hydrogen
combustion gas is adjusted to a total hydrogen
flow of 30 mL/min. Nitrogen can be added as
make-up gas, which increases sensitivity and
stability slightly. Detector temperature must al-
ways be kept above 150 ◦ C to prevent conden-
sation of water produced in the combustion pro-
cess. Flame tip and electrodes should be cleaned
36 Gas Chromatography
Table 4. Characteristics of common GC detectors

Name Type Selectivity Minimum detectability Linear

range
Flame ionization detector (FID) universal c a
10 pg C/s 107
Thermal conductivity detector (TCD) universal c b
1 ng/mL mobile phase 106
Electron capture detector (ECD) selective compounds capturing 0.2 pg Cl/s 104
electrons, e.g., halogens
Nitrogen phosporus detector (NPD) selective N and P 1 pg N/s 0.5 pg P/s 104
Flame photometric detector (FPD) selective P and S 50 pg S/s 103
2 pg P/s 104
Photoionization detector (PID) selective aromatics 5 pg C/s 107
Electrolytic conductivity detector (ELCD) selective halogens and S 1 pg Cl/s 106
5 pg S/s 104
Fourier transform infrared spectroscopy (FTIR) universal c molecular vibrations 1 ng (strong absorber) 103
Mass spectroscopy (MS) universal c characteristic ions 1 ng full-scan mode 105
1 pg ion-monitoring mode
Atomic emission detection (AED) universal c any element 0.2 – 50 pg/s depending on element 104
a
FID responds to all organic compounds that ionize in a flame.
b
TCD responds if thermal conductivity is different from carrier gas.
c
Spectroscopic detectors that can be operated in a universal or a selective mode.

regularly because certain compounds can cause
deposits that must be removed mechanically to
prevent loss in sensitivity and detector stabil-
ity. Bleeding of stationary phases and the use
of derivatization agents are important sources
of sensitivity loss and spikes. The flame shape
for capillary columns should be optimized, and
therefore flame tips with different bores are
available. Small-bore jets produce the greatest
signal for capillary GC.
6.2.2. Thermal Conductivity Detector
The thermal conductivity detector (TCD), also
called the hot-wire detector or katharometer,
measures the change in the thermal conductiv-
ity of the mobile-phase stream. Helium is the
recommended carrier gas because of its high
thermal conductivity. When an analyte is present
in the carrier gas, the thermal conductivity will
drop and less heat is lost to the cavity wall.
A filament in the detector cell operated under
constant voltage will heat up and its resistance
will increase. This resistance is measured and
recorded.
In the original TCD design the resistance
is incorporated in a Wheatstone bridge cir-
cuit. The difference in thermal conductivity bet-
ween the column effluent R1 and a reference
flow R2 is recorded. This original design is
still used in packed column GC (e.g., in pro-
cess control). Nowadays, single-filament, flow-
modulated thermal conductivity detectors are
available for capillary work. The cell size is
reduced to 3.5 µL to minimize detector band
broadening, and the single filament measures
the reduction in voltage required to maintain a
constant filament temperature. A diagram of a
commercially available TCD cell is presented
in Figure 36. In Figure 36 A, the switching flow
pushes the column effluent through the fila-
ment channel. On changing the switching flow
(Fig. 36 B), the column effluent passes through
the empty channel while the filament channel
fills with the pure reference gas. Switching bet-
ween column effluent and reference gas occurs
every 100 ms. An important parameter in practi-
cal work is the detector temperature. The lower
the temperature, the higher is the sensitivity
and the longer the lifetime of the filament. The
temperature must, however, be high enough to
avoid condensation of the solutes in the detector
cell. Oxygen-contaminated carrier gas, column
bleeding, and active components such as strong
acids and bases all decrease sensitivity and re-
duce the lifetime of the filament. Note also that if
helium is the carrier gas, and hydrogen together
with some other solutes must be measured, the
hydrogen peak will be negative because its ther-
mal conductivity is higher than that of helium,
while the other solutes give positive peaks.

Figure 36. Diagram of a miniaturized TCD cell
A) Measurement of column effluent flow; B) Measurement of reference flow
6.3. Selective Detectors
6.3.1. Electron Capture Detector
One of the most popular selective GC detec-
tors in use today is the electron capture detector
(ECD). The ECD is an extremely powerful tool
in environmental and biomedical studies. The
principle is based on the fact that electronegative
organic species (RX) react with low-energy ther-
mal electrons to form negatively charged ions.
The loss of electrons from the electron stream
that is measured is related to the quantity of an-
alyte in the carrier gas stream. The capturable
electrons originate from ionization of the car-
rier gas or a make-up gas (usually nitrogen or
an argon – methane mixture 95 : 5 or 90 : 10) by
β particles from a radioactive source such as
63
Ni placed in the cell. The electron flow re-
sults in a current that is measured. Electroneg-
ative species in the carrier gas capture elec-
trons and decrease the current. The highest sen-
sitivity is noted for organic polyhalides such as
Gas Chromatography 37
trihalomethanes, organochloropesticides, PCBs,
dioxins, and furans. Sensitivity increases in the
order F < Cl < Br < I. The selectivity depends
strongly on the compound’s affinity for elec-
trons and for polyhalides it is as high as 106
compared to hydrocarbons, and 104 compared
to ketones, anhydrides, amines, etc. By chemi-
cal derivatization, the applicability of ECD can
be expanded for trace analysis of species that do
not or only weakly capture electrons. The best-
known reagents are pentafluorobenzoic acid an-
hydride and pentafluorobenzoyl chloride for the
derivatization of alcohols, amines, and phenols.
(The fluorocompounds are chosen because of
their high volatility, even though the detec-
tor is less sensitive for fluorine.) The deriva-
tives formed are generally stable and have good
chromatographic properties. As an example, the
EPA method for the determination of chlorophe-
nols in water samples includes a derivatization
step with pentafluorbenzoyl chloride followed
by ECD detection, in this way enhancing both
38 Gas Chromatography

sensitivity and selectivity. For proper use of the

ECD detector, the carrier gas and the make-up
gas must be very clean and dry. In packed col-
umn GC, nitrogen or argon – methane is used as
carrier gas and no make-up gas is required at
the column outlet. In capillary GC, helium or
hydrogen is the preferred carrier gas because of
the speed of analysis, and 25 – 30 mL/min nitro-
gen or argon – methane is added as make-up gas
to produce the thermal electrons. The column
should also be preconditioned before connection
to the detector. High stability and sensitivity are
guaranteed only with the detector in constant op-
eration. Contamination is normally corrected for
by baking out the detector at 350 ◦ C over a 24-h
period. Some typical ECD chromatograms are
shown in Figure 37 for the direct analysis of tri-
halomethanes in drinking water [57] and in Fig-
ure 38 for the determination of organochloropes-
ticides.

Figure 38. Analysis of organochloropesticides with ECD

detection
Column: 20 m L×0.32 mm i.d.; 0.25 µm d f 7 % CPSi, 7 %
PhSi, 84 % MeSi (tailor-made called 1701); temperature:
180 – 240 ◦ C at 4 ◦ C/min; carrier gas hydrogen 8 psi
(≈ 5.6×104 Pa); ECD
Peaks: (1) HCB, (2) hexachlorocyclohexane, (3) lindane,
(4) heptachlor, (5) aldrin, (6) heptachlorepoxide,
Figure 37. Direct analysis of trihalomethanes in drinking
(7) α-endosulfan, (8) 1,1-dichloroethenylidenbis(4-
water
chlorobenzene), (9) dieldrin, (10) endrin, (11) 2,4-DDT,
Column: 30 m L×0.53 mm i.d.; 2.65 µm d f MeSi; retention
(12) β-endosulfan, (13)1,1 -(2,2-dichloroethylidene)bis(4-
gap 1.5 m L×0.53 mm i.d.; temperature: 50 – 150 ◦ C at
chlorobenzene),(14) 4,4 -DDT, (15) methoxychlor
10 ◦ C/min; cool on-column injection; carrier gas 10 kPa
hydrogen; ECD
Peaks: (1) chloroform, (2) dichlorobromoform, (3) di-
bromochloroform, (4) bromoform

6.3.2. Nitrogen Phosphorus Detector
The nitrogen phosphorus detector (NPD), also
called the thermionic detector (TID) is similar
in construction to the FID. The detector is made
element specific for N and P because a source of
an alkali salt – salts of potassium and rubidium
are more commonly used – is positioned above
the flame jet. By careful control of the combus-
tion gases hydrogen and air, whose flow rates
are less than those for the normal FID, the ion-
ization of compounds containing no nitrogen or
phosphorus is minimized, while the ionization of
N- and P- containing compounds is increased.
The exact mechanism is still unknown. Small
changes in detector gas flows have a signifi-
cant effect on sensitivity and selectivity. Opti-
mal gas flows can be found by analyzing a mix-
ture containing azobenzene, heptadecane, and
malathion in the ratio 1 : 1000 : 2 (100 pg/µL,
100 ng/µL, and 200 pg/µL, respectively). Promi-
nent responses shoin recent years uld be ob-
tained for azobenzene and malathion, whereas
the hydrocarbon should hardly be detected. Op-
timal flow rates on the order of 4 – 10 mL/min for
hydrogen and 60 –100 mL/min for air are typi-
cal. For some versions of the NPD detector the
use of a make-up gas such as helium increases
the N or P response. The NPD detector is a valu-
able tool in clinical and pharmaceutical analy-
sis, and especially in environmental monitoring
of organophosphorus- and organonitrogen- con-
taining pesticides.
6.3.3. Flame Photometric Detector
The flame photometric detector (FPD) uses the
principle that sulfur- and phosphorus-containing
compounds emit light by chemiluminescence
when burned in a hydrogen-rich flame. For
sulfur, for example, electronically excited di-
atomic sulfur (S∗2 ) is formed, which upon re-
laxation emits light over the wavelength region
320 – 450 nm, with an emission maximum at
394 nm. An optical filter at 394 nm permits the
light to enter a photomultiplier, and a signal is
produced. For phosphorus the interference fil-
ter is 526 nm. Although widely used mainly as a
sulfur-selective detector in the petroleum indus-
try, for the analysis of flavors and fragrances, in
environmental analysis, etc., the FPD detector
Gas Chromatography 39
has far from ideal characteristics as a GC de-
tector. It has many shortcomings; the most im-
portant one is that the intensity of light emit-
ted is not linear with concentration, but approx-
imately proportional to the square of the sul-
fur atom concentration. Careful calibration is
a must when quantitation is aimed at. Other
negative aspects are that the flame extinguishes
when high amounts of solvents are introduced
(this problem is eliminated when a dual-flame
burner is used), hydrocarbon quenching occurs,
and self-quenching occurs at high concentra-
tions of the heteroatom species. Moreover, op-
timization of the different flows is very criti-
cal for optimal sensitivity and selectivity. There-
fore, for the analysis of sulfur-containing com-
pounds the FPD detector is often replaced by the
atomic emission detector, the Hall electrolytic
conductivity detector, or the chemiluminescence
detector based on ozone reactions, whereas for
organophosphorus compounds the NPD is pre-
ferred.
6.3.4. Overview of Other Selective Detectors
Two of the more recently developed detectors,
namely, the Hall electrolytic conductivity de-
tector (ELCD) and the photoionization detec-
tor (PID) are recommended by the EPA for the
analysis of volatile and semivolatile halogenated
organic compounds and low molar mass aromat-
ics. Chemical emission based detectors, such as
the thermal energy analyzer (TEA) for its deter-
mination of nitrosamines and the redox chemilu-
minescence detector (RCD) for the quantitation
of oxygen- and sulfur- containing compounds,
are becoming more and more important for some
typical applications.
6.4. Detectors Allowing Selective
Recognition
The selective detectors discussed in the previous
sections often do not provide enough informa-
tion to elucidate with 100 % probability the na-
ture of the eluting solutes. For this reason, data
with selective detectors can be erratic. The fu-
ture in this respect definitely belongs to the spec-
troscopic detectors that allow selective recogni-
tion of the separated compounds. Today, the hy-
phenated techniques CGC – mass spectroscopy
40 Gas Chromatography
(CGC – MS), CGC – Fourier transform infrared
spectroscopy (CGC – FTIR), and CGC – atomic
emission detection (CGC – AED) are the most
powerful analytical techniques available. They
provide sensitive and selective quantitation of
target compounds and structural elucidation or
identification of unknowns. The applicability
and ease of use of the hyphenated techniques
were greatly increased by the introduction of
fused silica wall coated open tubular columns.
The main reason for this is that because of the
low flows of capillary columns, no special in-
terfaces are required and columns are connected
directly to the different spectrometers. The intro-
duction of relatively inexpensive benchtop hy-
phenated systems has enabled many laboratories
to acquire such instrumentation, which in turn
has expanded their applicability ever further.
The hyphenated techniques CGC – MS,
CGC – FTIR, and CGC – AED are generally
used as stand-alone units. Due to the nonde-
structive character of FTIR, CGC – FTIR – MS
units (Fig. 39) are possible and have been com-
mercialized. The software then allows simul-
taneous recording of the infrared and mass
spectra of the eluting compounds. In principle,
CGC – FTIR – MS – AED is also possible if an
open split interface is applied for the CGC –
FTIR – MS combination and the split-line is di-
rected into the AED detector. The fundamental
aspects of CGC – MS, CGC – FTIR and CGC –
AED are discussed in [58], [59], and [60].
Figure 39. Diagram of a capillary GC – FTIR – MS system
a) Capillary GC; b) FTIR; c) MS
6.4.1. Mass Spectrometry
The principle of CGC – MS is illustrated with
a quadrupole mass analyzer as an example. As
sample molecules exit the chromatographic col-
umn, they are introduced in the ion source of the
mass spectrometer and ionized. Depending on
the ionization method, molecular ions or frag-
ment ions are formed, which are accelerated
and separated from each other according to their
mass-to-charge ratios (m/z) by a mass analyzer
such as a quadrupole (c) (Fig. 40). Other mass
analyzers are magnetic sector instruments, ion
trap detectors, and time-of-flight mass spectrom-
eters. The separated ions are then detected by a
electron multiplier (d), and the resulting mass
spectrum is a line spectrum of intensity of ions
( y-axis) versus their m/z ratio (x-axis).
Two different ionization methods are avail-
able in CGC – MS, namely, electron ionization
(EI) and chemical ionization (CI). In electron
ionization, the molecules are bombarded with
electrons of 70 eV emitted from a rhenium or
tungsten filament. A molecular radical ion is
formed (M•+ ) with sufficient amount of energy
accumulated in its bonds to dissociate into typi-
cal fragment ions, radicals, and neutral species.
Since low ion source pressures are employed
(10−5 torr ≈ 1.33×10−2 Pa), reactions in the
ion source are unimolecular, and association
between molecule and fragment ions does not
occur. A disadvantage of electron ionization is
that energy in the molecule is so large that com-
plete fragmentation can occur and the molecular
ion is absent. Less fragmentation is obtained
with chemical ionization, which is a soft tech-
nique of ionizing molecules through gas-phase
ion – molecule reactions. In chemical ioniza-
tion, a reagent gas such as methane is introduced
into the ion source and a relatively high source
pressure is maintained (1 torr ≈ 133 Pa). The
reagent gas is ionized by the electrons, and the
ions formed interact with the sample molecules.
Since these reactions are low in energy, abundant
quasi-molecular ions, most often M•+ + 1 are
observed. Figures 41 and 42 show the electron-
impact and the chemical-ionization spectra of
trimethylsilylated clenbuterol. Chemical ioniza-
tion is very useful to elucidate the molecular ion
of unknowns and is often the ionization method

Figure 40. Schematic of a capillary GC – MS system
a) Capillary column; b) Ion source; c) Quadrupole mass filter; d) Multiplier
of choice for quantitative mass spectroscopy via
ion monitoring. After ionization, the positive
ions are accelerated and separated in the mass
analyzer by tuning the voltage on the quadrupole
rods. An ion of unit mass will pass the rods and
reach the detector only if the voltages are prop-
erly adjusted. To detect all ions, the voltage is
varied in time, and the time to detect all ions
is called a scan. This means that if all ions bet-
ween mass 20 and 400 are to be detected in 1 s,
the voltages are on the exact value for each ion
to pass during 1/380 of a second. This mode,
called the full-scan mode, is necessary to iden-
tify compounds via their fragmentation pattern.
Data are acquired by continuous repetitive scan-
ning of the column eluate. The reconstructed
chromatogram of a mass spectrometer is a plot
of the total ion current as a function of time
or scan number. All recorded spectra or scans
are stored in the computer and can be recalled
for identification. Nowadays this is performed
mostly by comparison with a spectral library.
The information in the stored mass scans can
provide, in a simple way, valuable information
on specific compounds or compound classes.
This is illustrated in Figure 43, which shows the
reconstructed total ion chromatogram of a sol-
vent mixture (Fig. 43 A) and the reconstructed
chromatogram of three specific ions typical for
C3 (trimethyl or methylethyl), C4 (tetramethyl,
dimethylethyl, diethyl, etc.), C5 (pentamethyl,
trimethylethyl, dimethylpropyl, etc.) benzenes
(Fig. 43 B – D). This is called mass chromatog-
raphy, and only data stored in the computer
of the full-scan mode are used to provide se-
lectivity. Mass fragmentography or selected ion
monitoring (SIM), on the other hand, is a method
to quantify target compounds with high selec-
tivity and sensitivity. In this mode of operation,
the voltages on the quadrupole rods are adjusted
Gas Chromatography 41
stepwise to detect only two, three, or four ions.
The time the rods are on a particular voltage
to let an ion pass is much longer than in the
case of the full-scan mode, which results in
enhanced sensitivity. As an illustration, in the
previous case for the full-scan mode, each ion
was seen for only 1/380 of a second. Suppose
clenbuterol has to be quantified. By selecting
the ions 259 and 349 only (Fig. 42), each ion
is detected in a 1-s scan for 1/2 s. Compared to
the full-scan mode, the residence time is 190
times higher; thus the sensitivity increases by
a factor 190. With modern CGC – MS systems,
picogram amounts can easily be quantified when
operated in the ion-monitoring mode. An inter-
esting feature of SIM is that internal standards
can be selected that chemically, physically, and
chromatographically behave exactly the same
as the compound to be measured. In the case of
clenbuterol, for example, the best internal stan-
dard is D6 - clenbuterol with typical ions at m/z
265 and 355. In routine analysis, D6 - clenbuterol
is added to the sample (i.e., urine) before any
pretreatment. Sample preparation and cleanup
are then performed, and the four ions 259 and
349 for clenbuterol and 265 and 355 for the
internal standard D6 - clenbuterol are recorded.
Quantitation is very easy.
6.4.2. Fourier Transform Infrared
Spectroscopy
In the combination CGC – FTIR, IR spectra of
the eluting peaks are recorded as they emerge
sequentially from the column outlet. The elu-
ate is introduced in a light pipe where com-
pounds absorb radiation at well-defined frequen-
cies (i.e., frequencies characteristic of the bonds
within a molecule). The absorption is sensed and
recorded. The sensitivity of FTIR depends on the
42 Gas Chromatography
Figure 41. Electron ionization spectrum of TMS – clenbuterol
Figure 42. Chemical ionization spectrum (reagent gas isobutane) of TMS – clenbuterol
functionalities within a molecule, and for strong
IR absorbers, 1 ng yields a good spectrum. Cur-
rent FTIRs include computers, and the recorded
spectra can be compared with a library of spectra
to aid in compound identification. Monitoring of
specific wavelengths allows the elucidation of
classes of compounds (e.g., aldehydes, ketones,
alcohols, ethers). On-line coupling of CGC –
FTIR and CGC – MS can be realized in series
since the FTIR is nondestructive. The IR spectra
are complementary in nature to MS spectra, es-
pecially for the elucidation of isomers for which
MS is not very informative. A typical example
is the determination of impurities in α-angelica
lactone. Figure 44 shows the total response chro-
matogram obtained with FTIR and the total ion
chromatogram, recorded by the mass spectrom-
eter. Both chromatograms correspond very well,
and at any time MS and IR data can be recalled
and compared. The mass spectra of peak 1 and
2 are very similar and do not allow the differ-
entiation of structural differences. The infrared
 Gas Chromatography 43

Figure 43. Illustration of mass chromatography

A) Solvent mixture; B) C3 -Benzene; C) C4 -Benzene; D) C5 -Benzene

spectra of peak 1 and 2 are compared in Fig-
ure 45. Some important differences are noted.
The shift of the carbonyl band from 1833 cm−1
(peak 1) to 1806 cm−1 (peak 2) indicates that
peak 2 corresponds to β-angelica lactone (α, β-
unsaturated instead of β, γ-unsaturated).
6.4.3. Atomic Emission Detection
One of the latest developments in hyphenated
techniques is the atomic emission detector. The
availability of a bench-top model CGC –AED
44 Gas Chromatography

Figure 44. Capillary GC – FTIR – MS chromatograms of α-angelica lactone

A) Total response chromatogram (FTIR); B) Total ion chromatogram (MS)

Figure 45. Infrared spectra of peak 1 and 2 of chromatogram in Figure 44

enables the use of this powerful technique in
routine analysis. Detectabilities of this element-
specific detector are of the order of 0.1 pg/s for
organometallic compounds, 0.2 pg/s for carbon
(more sensitive than FID), 1 pg/s for sulfur, and
15 pg/s for nitrogen, to mention only a few. The
power of the technique lies in its supreme selec-
tivity: all elements can be detected selectively.
As opposed to ECD, AED allows differentia-
tion between various halogenated organic com-
pounds (e.g., fluoro, chloro, and bromo compo-
nents). Multielement analysis can be carried out
by simple preselection of the atoms to be moni-
tored. In AED, the solutes eluting from the col-
umn are atomized in a high-energy source; the
resulting atoms are in the excited state and emit
light as they return to the ground state. The var-
ious wavelengths of the emitted light are then
dispersed in a spectrometer and measured by
using a photodiode array. Each element has a
typical emission spectrum, with emission lines
commonly occurring in clusters. The relative in-
tensities of lines within these clusters are con-
stant. Figure 46 shows the emission spectrum of
a sulfur- containing compound, and the 180.7-,
182.0-, and 182.6-nm cluster serves as conclu-
sive proof of the presence of sulfur in a peak.
Multiwavelength detection became possible
through the introduction of diode array technol-
ogy. Quantitative treatment of the data obtained
in a multielement analysis moreover allows the
calculation of empirical formulas, yielding in-
formation that is complementary to and helpful
in the interpretation of mass spectral data. Quan-
titation is simplified considerably, since calibra-
tion of the detector no longer depends on the
type of components to be quantified. Nontoxic
compounds can thus be used to quantify harmful
chemicals. Figure 47 illustrates the sensitivity
of the detector for organometallic compounds.

Figure 46. Emission spectrum of a sulfur-containing compound
Organolead halides are derivatized with butyl-
magnesium bromide into tetraalkylated solutes,
which are amenable to CGC analysis. By se-
lecting a wavelength of 406 nm, high selectivity
and sensitivity (10 pg per compound) are guar-
anteed. Another important application concerns
direct monitoring of oxygenates in petroleum
products. Figure 48 shows the direct analysis of
a light naphtha containing low concentrations
(ppm) of oxygenated compounds. The concen-
trations for methanol and ethanol are 100 and
50 ppm, respectively.
7. Practical Considerations in
Qualitative and Quantitative
Analysis
A chromatogram provides information on the
complexity (number of peaks), identity (reten-
tion time), and quantity (peak area or height) of
the components in a mixture. This information
can be considered suspect if the quality of sep-
aration is not optimal. Capillary columns have
greatly enhanced the use of gas chromatography
as a qualitative and quantitative tool.
7.1. Qualitative Analysis
Modern capillary GC is characterized by very
good precision in retention time, and this allows
the use of retention indices for peak identifi-
cation. In a retention index system, the reten-
tion behavior of a particular solute is expressed
Gas Chromatography 45
in a uniform scale determined by a series of
closely related standard substances. In the reten-
tion index scale developed by Kovats [61] for
isothermal separations and by Van den Dool
and Kratz [62] for temperature-programmed
analyses, the fixed points of the scale are nor-
mal alkanes. The Kovats retention index system
is illustrated in Figure 49. Compound X elutes
between the hydrocarbons hexane and heptane
with carbon numbers 6 and 7, respectively. For
convenience, the carbon numbers are multiplied
by 100, thus 600 and 700. The retention index I x
of compound X is 673.8. Indices are not graphi-
cally measured but calculated by Equation (7.1)
logtRx −logtRz
Ix = 100z +100 (7.1)
logtRz+1 −logtRz
where z is the carbon number of the n-alkane
eluting before X; z + 1 is the carbon number of
the n-alkane eluting after X; and t R is the ad-
justed retention time.
To perform the interpolation, the adjusted re-
tention times of the n-alkanes must be known.
This is often done by analyzing a separate mix-
ture containing n-alkanes. This requires, how-
ever, automated injection. For manual injection,
n-alkanes are added to the sample. In Equa-
tion (7.1), logarithmic interpolation is necessary
because the adjusted retention times increase ex-
ponentially with carbon number (Eq. 4.1). In lin-
ear temperature-programmed runs, the retention
times of a homologous series (i.e., the n-alkanes)
increase linearly with carbon number, and the
46 Gas Chromatography
Figure 47. AED analysis of organolead compounds
Figure 48. AED analysis of light naphtha in the C (A) and the O (B) emission line
equation for temperature-programmed analysis
is simplified to
tRx −tRz
Ix = 100z +100
tRz+1 −tRz
Unadjusted retention times may be used. The
isothermal indices depend on the stationary
phase and film thickness and on the tempera-
ture. Specification of those variables is a must.
The programmed indices, often called linear
retention indices, require specification of the
temperature profile as well. Once determined,
the indices can be used to identify compounds
from libraries with tabulated indices [63], [64].
The general utility of those libraries for iden-
tification is questionable. Indices are best used
within a laboratory for specific samples (i.e., pe-
(7.2) troleum products, essential oils, steroids, etc.).
Greater confidence in identification is obtained
by measuring indices on more than one station-
ary phase. Unequivocal compound elucidation
requires spectroscopic characterization as pro-
vided by mass spectroscopy, Fourier transform
infrared spectroscopy, and atomic emission de-
tection.
Recently, the concept of retention time lock-
ing was introduced, and this opens new perspec-

Figure 49. The Kovats retention index system
tives in capillary GC for solute elucidation (see
Section 10.2).
7.2. Quantitative Analysis
Four techniques are commonly used in quanti-
tative analysis: the normalization method, the
external standard method, the internal stan-
dard method, and the standard addition method.
Whatever method is used, the accuracy often
depends on the sample preparation and on the
injection technique. Nowadays these are two
main sources of error in quantitative analysis.
The quantitative results produced by PCGC and
CGC are comparable.
8. Coupled Systems
Coupled systems include multidimensional and
multimodal systems. Multidimensional chro-
matography involves two columns in series
Gas Chromatography 47
preferably two capillary columns, with differ-
ent selectivity or sample capacity, to optimize
the selectivity of some compounds of interest in
complex profiles or to provide an enrichment
of relevant fractions. In multimodal systems,
two chromatographic methods or eventually a
sample preparation unit and a chromatographic
method are coupled in series. Coupled systems
that received much interest in recent years are
multidimensional CGC (MDCGC), the combi-
nation of high-performance liquid chromatogra-
phy with CGC (HPLC – CGC) and the on- or off-
line combination of supercritical fluid extraction
with CGC (SFE – CGC). Multidimensional and
multimodal techniques in chromatography are
described in detail in [65].
8.1. Multidimensional Capillary GC
For highly complex samples, the separation
power of a single capillary column is insuffi-
cient to achieve complete resolution for the com-
pounds of interest. Even after optimization of
48 Gas Chromatography

Figure 50. Multidimensional CGC analysis of pepermint oil, two column system constant pressure – constant pressure
A) Separation on MeSi; B) Analysis on MeSi after heartcut ; C) Analysis of heartcut fraction on column B with intermediate
trapping; D) Analysis of heartcut fraction on column B without intermediate trapping (selectivity tuning)
Column A : 20 m L×0.32 mm i.d.; 0.24 µm d f MeSi
Column B : 20 m L×0.32 mm i.d.; 0.24 µm d f high-M r PEG
Temperature: 60 ◦ C (2 min) to 180 ◦ C at 3 ◦ C/min; split injection 1/50; carrier gas hydrogen; FID

Figure 50. (Continued)
the selectivity, important compounds will still
coelute, since the better separation of one pair
of compounds is likely to be counteracted by
the overlapping of another pair of compounds
present in the sample. The only solution is the
combination of more than one column system. In
multidimensional CGC, a group of compounds
that has not been separated on a first column is
transferred (heartcut) to a second column, where
complete resolution is achieved. Two opera-
tional modes can be distinguished. If the trans-
ferred fraction is coldtrapped before analysis on
the second column (intermediate trapping), the
selectivities of both columns are decoupled. The
elution of the transferred solutes will be inde-
pendent of the selectivity of the first column and
will be the same as if the pure sample com-
pounds were analyzed on the second column
only. Alternatively, when no intermediate trap-
ping is applied, the elution pattern observed after
analysis on the second column will be the same
as the elution pattern for analysis on a mixed-
phase column or a coupled column system with
an intermediate selectivity between the selec-
tivities of both columns. Both principles are il-
lustrated in Figure 50. Peppermint oil was ana-
lyzed on a methylsilicone capillary column, and
the separation of the menthone – menthol frac-
tion (peak 1 – 7) is incomplete (Fig. 50 A). This
fraction was heartcut (Fig. 50 B) and further an-
alyzed on a poly(ethylene glycol) capillary col-
umn. With intermediate trapping (Fig. 50 C) the
Gas Chromatography 49
separation is drastically improved, but the high-
est resolution, in this case, is without interme-
diate trapping (Fig. 50 D). This is an illustration
of the power of multidimensional CGC in com-
bination with selectivity tuning.
Developments in multidimensional CGC di-
verge in two main directions: the coupling of
narrow to narrowbore capillaries to enhance res-
olution, on the one hand, and the coupling of
widebore precolumns to narrowbore capillaries
as a selective sample introduction method, on
the other. Some inlet devices, such as the pro-
grammed temperature vaporization injector op-
erated in the solvent vent mode, can also be
classified as multidimensional systems. The sol-
vent is removed through the split vent, while
the solutes of interest remain in the liner. The
multidimensional approach with selective sam-
pling is of considerable interest in routine anal-
ysis. It allows preseparation of relatively large
amounts of sample on the precolumn operated
under constant-flow conditions. Fine-tuning of
the separation can be achieved on the analytical
column, operated in the constant-pressure mode.
The system is easy to operate and can be installed
without problems in every GC instrument. Sys-
tems based on constant pressure – constant pres-
sure and constant flow – constant flow offer more
flexibility because column dimensions are less
critical than in the constant flow – constant pres-
sure system; however, they are expensive and re-
quire time-consuming optimization procedures
50 Gas Chromatography
when new applications are carried out. The pos-
sibilities of multidimensional capillary GC as a
sampling method are illustrated with the analy-
sis of volatiles emitted by living plants [66]. The
atmosphere surrounding a plant (headspace) is
sucked in an open tubular trap (3 m in length,
530 µm i.d.) coated with a 15-µm film of methyl-
silicone where the volatiles are retained by the
normal chromatographic partitioning process at
ambient temperature. The advantages over traps
filled with adsorbents are that breakthrough vol-
umes can be calculated, the inertness is high,
and thermal desorption of polar compounds is
feasible. After sampling, the trap is installed as
precolumn in a multidimensional CGC system
(Fig. 51). The volatiles are thermally desorbed,
reconcentrated in a cold trap (e), and then ana-
lyzed on-line on the analytical capillary column
(f ). Figure 52 shows the headspace CGC – MS
analyses of a healthy and a fungus-infected Men-
tha arvensis plant. Menthol (peak 15) is the main
compound in the healthy plant (Fig. 52 A), and
the highly volatile fraction is relatively poor. In
the infected plant (Fig. 52 B), menthyl acetate
(peak 21) is the main compound, while the rel-
ative percentage of menthone (peak 13) is in-
creased and the highly volatile fraction is more
abundant. This hyphenated combination live
headspace sampling – multidimensional capil-
lary GC – MS provides interesting results in phy-
tochemical research. In 1992, a more sophis-
ticated system, PTV injection –MDCGC with
three columns –MS was described for the anal-
ysis of dioxins and furans [54].
8.2. Multimodal High-Performance
Liquid Chromatography – Capillary GC
The on-line coupling of HPLC to capillary GC
has received much attention since the mid-
1980s. Pioneering work was performed by
K. Grob, Jr. [67]. The coupling of HPLC to cap-
illary GC can be considered as an on-line sample
preparation and enrichment step. Preseparation
can be carried out according to molecular mass
(SEC), functionality (straight-phase LC), or hy-
drophobicity (reversed-phase LC). Similar re-
sults are obtained with off-line techniques (i.e.,
solid-phase extraction or LC off-line fraction-
ation), but advantages of the on-line approach
include easier automation, fewer artifacts, and
higher sensitivity because the total elution vol-
ume of the fraction of interest is transferred to
the capillary GC column.
A fully automated and flexible on-line
LC – GC system has been described [68]. The
system is based on standard LC and capillary GC
instrumentation. The on-line LC – GC system
was evaluated for the determination of pesticides
in orange oil. The essential oil was fractionated
by normal-phase LC, resulting in a separation
according to polarity. The fraction containing
pesticides was transferred and analyzed by capil-
lary GC – NPD. The LC – GC interface is a mod-
ified large-volume sampler (Gerstel, Mulheim
a/d Ruhr, Germany). The heart of the system is
a specially designed flow cell that replaces a nor-
mal vial. The mobile phase leaving the LC de-
tector is directed via a capillary tube with well-
defined dimensions into a T-shaped flow cell.
The cell is equipped with a septumless sampling
head through which a syringe needle can be in-
troduced. The sampler is completely computer
controlled. To transfer a selected LC fraction, the
transfer start and stop times, measured on the LC
chromatogram, are introduced into the controller
software. The time delay between the LC detec-
tor and the flow cell is automatically calculated
from the dimensions of the connecting tubing
and the LC flow rate. When the LC fraction of
interest passes through the flow cell, the syringe
needle penetrates the septumless head and sam-
ples the LC fraction at a speed equal to the LC
flow rate. Up to 2 mL can be collected in the sy-
ringe. After collection, the needle is withdrawn
from the flow cell, which rotates away from the
PTV inlet, and a large-volume injection is made
by using the PTV in the solvent-vent mode. De-
pending on the fraction volume and solvent type,
the sample introduction parameters (inlet tem-
perature, vent flow, vent time, injection speed,
etc.) are calculated by the PTV calculator pro-
gram. For fractionation of the orange oil sam-
ple, the following HPLC parameters were used:
column 250 mm × 4.6 mm i.d. × 10 µm Lichro-
spher 100 DIOL, injection volume 20 µL, mo-
bile phase in a gradient from 100 % hexane
for 10 min, to 40 % isopropyl alcohol at 20 min
(2 min hold) at a flow rate of 1 mL/min and UV
detection at 220 nm. The fraction eluting from
4.4 – 4.9 min (volume = 0.5 mL) was automati-
cally transferred to the GC inlet. The LC – GC
interface was programmed to take the sample at a
 Gas Chromatography 51

Figure 51. MDCGC system constant flow – constant pressure

a) Injector; b) Precolumn; c) Detector 1; d) Switching device; e) Cold trap; f ) Analytical column; g) Detector 2

Figure 52. CGC pattern of the head space of a healthy (A) and an infected (B) Mentha arvensis plant
Thermal desorption and cryofocusing
52 Gas Chromatography
Figure 53. LC fractionation of orange oil on Lichrosorb 100 DIOL
Figure 54. Overlay of relevant parts of LC chromatograms of a 1 ppm ethion standard (bottom trace) and orange oil (top trace)
sampling speed of 1000 µL/min (the same as the
LC flow rate). The complete fraction of 500 µL
was injected in the PTV inlet at 250 µL/min.
This injection speed corresponds to the injec-
tion speed calculated by the PTV software pro-
gram. Capillary GC – NPD analysis was per-
formed on a 30 m × 0.25 mm i.d. × 0.25 µm
MeSi column and the oven was programmed
from 70 ◦ C (2 min) to 150 ◦ C at 25 ◦ C/min and
then to 280 ◦ C at 8 ◦ C/min (10 min). The detec-
tor was set at 320 ◦ C with 3 mL/min hydrogen,
80 mL/min air, and 30 mL/min helium make-up
flow.
The LC profile for the orange essential oil
is shown in Figure 53. The apolar mono- and
sesquiterpenes elute first, followed by the ter-
penoids and after 16 min also the flavanoids are
eluted. These last compounds in particular give
most interference in GC analysis because they
have similar molecular weights to the pesticides.
Using the same conditions, ethion and chlorpy-
riphos elute at 4.6 – 4.7 min. Figure 54 shows a
comparison of the analysis of a 1 ppm ethion
reference sample and the essential oil analysis.
The fraction eluting from 4.4 to 4.9 min
was transferred to the CGC-NPD and analyzed.
Figure 55 shows the resulting GC – NPD chro-
matogram and both ethion and chlorpyriphos
(t R 15.79 min) are detected. The chromatograms
are very clean and no interferences are present.
This demonstrates the excellent selectivity of
the LC – GC combination. The concentrations
of ethion and chlorpyriphos were calculated by
external standard analysis and are 1.9 ppm for
chlorpyriphos and 0.8 ppm for ethion.
8.3. Multimodal Supercritical Fluid
Extraction – Capillary GC
Because supercritical fluids have excellent char-
acteristics for the rapid extraction of organic
 Gas Chromatography 53

Figure 55. LC – Capillary GC – NPD analysis of orange oil

compounds, combining supercritical fluid ex- placed in the extraction vessel, and 250 µL of
traction with CGC is an interesting approach to methanol was added on top of the sediment.
the enrichment of organic solvents [69], [70]. SF extraction was performed at 60 ◦ C with pure
Since the density of supercritical fluids –usually CO2 at 35 MPa for 30 min. The concentration of
carbon dioxide –can be varied (pressure, temper- the main compound dieldrin is 20 ppb. Classical
ature), a high degree of selectivity can be intro- Soxhlet extraction gave the same concentration.
duced in the sample preparation procedure (i.e.,
prior to the analytical system). The selectivity
can be further enhanced by making use of mod-
ifiers that may be polar (e.g., CO2 – MeOH) or
nonpolar (CO2 – hexane). The main applications
of SFE – CGC are related to solid samples, such
as soil or sediment samples, and plant materials.
For aqueous solutions (e.g., wastewater, urine),
samples are enriched by solid-phase extraction.
The extraction cartridges are then submitted to
SFE – CGC, thus providing all the advantages
of SFE (i.e., selective extraction and ease of au-
tomation). There is some controversy in the lit-
erature whether on-line SFE – CGC is the best
approach to the application of analytical super-
critical fluid extraction. Indeed off-line SFE has
some advantages, and the use of robotics allows
automated transfer of the sample to the capillary
GC instrument. Selection of on-line or off-line
depends mainly on the specific problem. Off-
line is preferred for method development and
on-line for routine analysis. On-line can, how-
ever, be recommended only when the matrix
from which the solutes have to be extracted is
always the same (e.g., in chemical composition,
particle size, pore size). Moreover, the literature
on SFE extraction times and recoveries is often
incorrect because spiked samples are analyzed.
Applied to real contaminated samples, SFE is Figure 56. Analysis of SFE extract of a sediment with ECD
found to be much more difficult. Figure 56 shows detection
the optimized off-line SFE – CGC analysis of Peaks: (1) aldrin, (2) dieldrin, (3) endrin
pesticides from sediment: 500 mg sediment was
54 Gas Chromatography
9. Applicability
9.1. Solute Thermal Stability
Solutes subjected to GC must be thermally sta-
ble. The thermostability of organic compounds
depends strongly on their nature, on the activity
of the environment in which thermal stability is
measured, and on the thermal stress given to the
solutes. Capillary GC nowadays is performed in
a completely inert system, i.e., highly pure car-
rier gas, purified stationary phases, fused silica
with less than 0.1 ppm metal traces and specially
deactivated, etc. Moreover, thermal stress can be
avoided by applying cool on-column injection.
Lipids serve as a good illustration. When oils or
fats are used in food preparation, they decom-
pose (formation of aldehydes etc.) or polymer-
ize (formation of dimers, trimers, etc.) as a func-
tion of time, which make them no longer useful
for cooking. These alterations are caused by the
presence of water and oxygen. When heated un-
der inert conditions, fats and oils are stable and
evaporate. Figure 57 compares the thermogravi-
metric profiles recorded for triolein (M r = 886)
under a stream of pure nitrogen gas (a) and
air (b). In present state-of-the-art GC, the sys-
tems are operated under circumstances shown
in curve a.
Figure 57. Thermogravimetric analysis of triolein
Ramp from 40 – 500 ◦ C at 5 ◦ C/min
a) Pure nitrogen; b) Air
9.2. Solute Volatility
Volatility is related to the vapor pressure
(boiling point) of the compounds. Polydi-
methylsiloxanes with molecular masses as high
as 5000 are volatile enough to be analyzed
by GC, whereas poly(ethylene glycols) with
M r of ca. 1500 are not volatile at all. Volatil-
ity is thus related not only to the molecu-
lar mass, but to the polarity of the functional
groups. Polydimethylsiloxane (M r 5000) has
approximately 68 apolar dimethylsiloxane units,
whereas poly(ethylene glycol) (M r 1500) has
114 polar ethoxy units besides the terminat-
ing hydroxyl groups. Some thermolabile com-
pounds, although able to be volatilized, un-
dergo partial decomposition at high tempera-
ture. Derivatization can be employed to im-
part volatility and to yield a more stable prod-
uct, thereby improving chromatographic perfor-
mance and peak shape. Three general types of
analytical derivatization reactions are used in
GC : alkylation, acylation, and silylation [71],
[72]. The ideal derivatization procedure must
be simple, fast, and complete. Alkylation, acy-
lation, and silylation are used to modify com-
pounds containing functional groups with ac-
tive hydrogens such as −COOH, −OH, and
−NH2 . The tendency of these functional groups
to form intermolecular hydrogen bonds affects
the inherent volatility of compounds containing
them, their interaction with the stationary phase,
and their stability. Figure 58 shows the analysis
of sucrose in molasses with capillary GC. Tre-
halose is used as internal standard, and the sam-
ple is derivatized into the oxime – trimethylsilyl
derivatives.
Figure 58. Capillary GC analysis of sugar derivatives
(oxime – TMS)
Column: 10 m L×0.53 mm i.d.; 0.1 µm d f MeSi; tempera-
ture: 80 – 300 ◦ C at 10 ◦ C/min; cool on-column injection;
carrier gas hydrogen 4 mL/min; FID
 Gas Chromatography 55

9.3. Comparison of Gas

Chromatography, Liquid
Chromatography, and Supercritical
Fluid Chromatography

When a scientist is faced with deciding which

separation technique to use for a specific ana-
lytical problem, the primary question is, which
chromatographic technique best suits this par-
ticular separation. The initial answer is dic-
tated by the chemical nature of the analytes
themselves. For the analysis of volatile compo-
nents, gas chromatography is preferred. For an-
alyzing strongly polar or ionic compounds, liq-
uid chromatography may be the best choice. In
some cases, supercritical fluid chromatography
has distinct advantages over GC and LC. How-
ever, for many applications – such as analyses
of polycyclic aromatic hydrocarbons, polychlo-
rinated biphenyls, lipids, fatty acids, steroids,
fat-soluble vitamins, mycotoxins, etc., – several
chromatographic techniques can be considered.
In such cases, strange as it may seem, the
choice of a chromatographic technique is often Figure 59. HPLC analysis of steroid esters
biased on secondary considerations such as the A) Column: 10 cm L×0.3 cm i.d., 5 µm ODS, flow
analyst’s know-how and skill or the availability 0.5 mL/min methanol – water 85 : 15, UV at 254 nm; B) see
of a particular instrument. This choice is usually A, light scattering detection
Peaks: (1) testosterone propionate, (2) testosterone
justified with supplementary arguments, espe- isocaproate, (3) testosterone phenylpropionate,
cially those concerning the simplicity of a tech- (4) testosterone decanoate
nique. Recent technical developments in nearly
all branches of chromatography, however, have A study was conducted in which the perfor-
largely overcome any “advantage of simplicity” mance of three techniques – high-performance
(to some, the “disadvantage of complexity”) of LC (HPLC), capillary GC (CGC), and capil-
various techniques. The extended possibilities lary SFC (CSFC) – was compared in the anal-
of automation further weaken arguments of this ysis of the percent composition of steroid esters
kind. in a pharmaceutical hormone formulation [73].
More important, especially when the analyt- The study used standard chromatographic con-
ical method must be applied routinely, is its ditions, applicable in every laboratory, and the
cost. This will be governed mainly by the price conditions were optimized so as to yield com-
of the instrument, columns, and mobile phases, parable analysis times of <30 min.
as well as maintenance costs. In this respect,
High-Performance Liquid Chromatogra-
the chromatographic techniques can be ranked
phy. In the pharmaceutical industry, analysis of
in increasing order of the prices of analysis:
steroid ester formulations is performed routinely
GC < LC < SFC.
by using HPLC. Figure 59 A shows the HPLC
From a practical viewpoint that disregards
chromatogram of the sample mixture applying
costs, the choice of method must be based on
UV detection at 254 nm. The steroid esters are
three fundamental aspects: separation efficiency,
baseline separated in 24 min. The column plate
accuracy of the analytical method, and total re-
number, calculated for testosterone decanoate,
quired analysis time. For some applications, the
is 4500, which corresponds to 45 000 plates per
specificity and sensitivity (detectability) of a
meter. With UV detection, allowance must be
technique are also important.
made for different response factors. Calibration
56 Gas Chromatography
Table 5. Calculated percent composition of steroid esters ∗

Compound HPLC CSFC CGC on-column Composition in

mixture, %
UV MD ∗∗

Testosterone propionate 15.13 11.93 10.98 11.98 12.00

Testosterone isocaproate 27.77 23.68 23.57 25.20 24.00
Testosterone decanoate 33.25 40.43 44.33 39.99 40.00
Testosterone phenylpropionate 23.38 23.96 21.11 23.83 24.00
Mean RSD, % 1.43 1.08 2.58 0.58
Analysis time, min 22.50 25.00 21.50 21.50

∗ All values calculated from uncorrected peak areas with response factors = 1.0; mean values of five experiments.
∗∗ MD = mass detector.

graphs, however, can be recorded only if pure

compounds are used, which was not the case in
this study. A response factor of 1.0 was, there-
fore, applied for the various steroid esters, giving
the quantitative data listed in Table 5. Very of-
ten, in practice, unknown compounds are present
in HPLC chromatograms, and quantitation is im-
possible using UV detection.

Figure 61. Capillary GC analysis of steroid esters

Column: 25 m L×0.25 mm i.d.; 0.15 µm d f MePhSi; tem-
perature: 60 – 300 ◦ C at 10 ◦ C/min; cool on-column injec-
tion; carrier gas hydrogen 15 psi (≈1 bar); FID
Peaks: see Figure 60

Calibration can be avoided by using universal

Figure 60. Capillary SFC analysis of steroid esters
Column: 20 m L×0.1 mm i.d.; 0.1 µm d f MeSi; tempera-
ture: 130 ◦ C; pressure 200 bar CO2 ; FID
Peaks: (1) testosterone propionate, (2) testosterone
isocaproate, (3) testosterone decanoate, (4) testosterone
phenylpropionate
HPLC detection systems, such as refractive in-
dex detection or light-scattering detection. Com-
pared to UV, however, both of these detectors are
less sensitive. Figure 59 B shows the analysis us-
ing light-scattering detection; the sample is five
times more concentrated than in the UV trace
in Figure 59 A. The chromatographic efficiency
was reduced by 20 %, to 3600 plates, because
of a detector contribution to band broadening.

The quantitative data, calculated using response
factors of 1, are listed in Table 5 in the column la-
beled MD (mass detector). The calculated com-
position corresponds well to the known sample
composition.
Capillary Gas Chromatography. Steroid
esters are thermally stable. They can be analyzed
easily by CGC. Figure 60 shows the analysis of
the sample with cold on-column injection. The
plate number for this conventional CGC column
operated at 130 ◦ C was 85 000 plates; analysis
time was 22 min. The quantitative results (re-
sponse factors = 1.0) are given in Table 5. The
data for cold on-column injection correspond
very well with the known composition of the
sample, and % RSD is < 0.8 % (n = 5) for all
the steroid esters.
Figure 62. High-speed capillary GC analysis ofsteroid es-
ters
Column: 2 m L×0.25 mm i.d.; 0.1 µm d f MePhSi; temper-
ature: 260 ◦ C; split injection 1/100; carrier gas hydrogen
0.1 psi (≈ 700 Pa); FID
Capillary Supercritical Fluid Chromatog-
raphy. In the mid-1980s, considerable progress
has been made in CSFC, and the technique
is now accessible for routine chromatography.
CSFC is claimed to have advantages compared
to GC. Because of the high solvating power
of CO2 , high molar mass compounds elute at
Gas Chromatography 57
much lower temperature, allowing better anal-
ysis of thermally labile compounds. Compared
with HPLC, for the same column, the speed of
analysis for SFC is roughly four times faster. In
addition, because of the lower viscosity of the
mobile phase, much longer columns can be used,
increasing the effective plate number. Universal
GC detectors can be applied, and combination
with hyphenated techniques such as mass spec-
trometry or Fourier transform infrared spectrom-
etry is easier. Analysis of the steroid ester sam-
ple on a 20 m×0.1 mm column is shown in Fig-
ure 61. In this run at constant density, the plate
number is only 5000. This illustrates one of the
disadvantages of CSFC. Theoretically the col-
umn should offer 150 000 plates, but at a mobile
phase velocity of only 0.2 – 0.3 cm/s. This corre-
sponds to an unretained peak time of 2.5 h, and
an analysis time for a compound eluting with a
k value of 3.5 (peak 3, testosterone decanoate)
of 7.3 h. Such analysis times are, of course, un-
acceptable. Therefore the column is operated far
above the optimal velocity (Figure 61, at 6 cm/s).
The slope of the H – u curve is very steep for the
20-m column, and the plate height at 6 cm/s is of
the order of 6 mm. Much faster separations can
be obtained on short capillary columns with in-
ternal diameters of ≈20 µm, but because of tech-
nical problems (especially with sample intro-
duction), quantitation is very difficult. Quantita-
tion of the steroid mixture with CSFC (Table 5)
yields higher % RSD values and less accurate re-
sults than either CGC or HPLC. The reason for
this lies mainly in the injection method (valve
split discrimination). Compared to conventional
HPLC, the primary advantage of SFC is the use
of the universal FID detector. The results pre-
sented in Table 5 show that all three techniques
can be applied to analysis of the steroid sam-
ple. The difference in chromatographic behavior
among HPLC, CGC, and CSFC is determined
mainly by the mobile-phase properties such as
density, diffusivity, viscosity, and polarity. When
using dimensionless parameters, equations can
be derived that are valid for the three different
types of mobile phases and independent of par-
ticle size (packed columns) or column diameter
(capillary columns) [74]. The reduced param-
eters will not be discussed in detail but show
clearly, as far as efficiency and speed of anal-
ysis are concerned, no other chromatographic
methods can compete with GC. Baseline sepa-
58 Gas Chromatography
ration of the steroid esters can be obtained on
a 2-m capillary column offering 7000 plates in
25 s (Figure 62). This is not a plea for gas chro-
matography. It is just an example to illustrate the
possibilities of different chromatographic tech-
niques for the application selected. Often, how-
ever, one might be surprised to see the enormous
effort spent in trying a separation with a particu-
lar technique, while the use of another technique
seems straightforward. Each chromatographic
technique has its own possibilities, and a good
understanding of their performance is a prereq-
uisite before selection for a particular applica-
tion can be justified.
10. Recent and Future Developments
10.1. Fast High Resolution Capillary GC
Since the introduction of gas chromatography,
there has been an ongoing interest in improv-
ing analysis speed. Increasing analysis speed in
capillary GC in the first instance is dictated by
the problem at hand, the primary objective be-
ing the complete separation of the compounds
in a mixture. In many cases, the plate number of
a capillary column is too high for a given sep-
aration problem, and the resolution may be im-
paired. Typical ways to shorten the analysis time
in this case are decreasing the column length
or increasing the carrier gas flow rate far above
the optimum. Recent alternatives include the use
of multichannel columns or multicapillaries and
flash GC.
Increasing analysis speed for complex pro-
files without impairing resolution can only be
realized by reduction of the internal diame-
ter and the length of the capillary column. A
10 m × 0.1 mm i.d. column offers the same reso-
lution as a 25 m × 0.25 mm i.d. column. Because
the column is 2.5 times shorter, the analysis time
is reduced drastically. Moreover, since the opti-
mum carrier gas velocity is higher and the H-
u curves are flatter for narrow bore columns,
higher average carrier gas velocities can be used
without loss of resolution. Presently, capillary
columns with internal diameters on the order of
100 µm are in the picture for routine operation
because state-of-the-art capillary GC instrumen-
tation allows installation of such small diame-
ter columns. This is illustrated with the analysis
of a diesel sample with baseline separation of
the biomarkers pristane and phytane from the
preceeding normal hydrocarbons on a standard
GC instrument (Fig. 63). The diesel sample was
diluted 10 times in cyclohexane, and 1 µL was
injected in the split mode (1/1000 split ratio).
The column was a 10 m × 0.1 mm i.d. × 0.1 µm
MeSi. The oven was programmed from 100 to
325 ◦ C at 75 ◦ C/min and held for 1 min (4 min
program). FID detection with a signal data ac-
quisition rate of 100 Hz was used.
An important obstacle to the use of nar-
row bore columns, however, is method devel-
opment and validation. When using narrowbore
columns, different operational conditions (inlet
pressure, split ratio, temperature program) have
to be used. Since little information is yet avail-
able on the use of fast capillary GC, the transfer
of standard validated operating procedures de-
veloped for conventional capillary columns into
operating procedures for narrow bore columns
might be difficult and will definitely hamper
their use in a routine environment. In this re-
spect, the development of method-translation
software [75], [76] was very helpful for trans-
lating a standard operating procedure for a con-
ventional column (whatever its dimensions and
stationary phase film thickness) to an operat-
ing procedure for a narrowbore column (coated
with the same stationary phase). After perform-
ing the analyses on the standard column, the
optimized conditions are introduced into the
method-translation program, and all operational
conditions for the new column are calculated
so as to obtain the same resolution. The gain
in analysis time is also predicted. The method-
translation software is available free of charge
from the Agilent website. The principle is il-
lustrated with the analysis of an essential oil.
Quality control of essential oil samples is rou-
tinely done on a 50 – 60 m × 0.25 mm i.d. col-
umn with a slow (2 ◦ C/min) temperature pro-
gram, which results in analysis times on the or-
der of 2 – 3 h. The same peak capacity can be ob-
tained on shorter narrowbore capillary columns,
but, although analysis times can be reduced dras-
tically, quality control laboratories hesitate to
use this approach because changing the column
dimensions implies different operational condi-
tions, which results in different selectivities. De-
tails of well-known fingerprints can be lost. The
application of the method-translation software

Figure 63. Separation of diesel oil in 2.5 min on standard GC instrumentation
allows the translation from conventional to nar-
rowbore columns with hardly any change in res-
olution, selectivity, and hence fingerprint. This
is illustrated with the analysis of nutmeg oil.
The analysis was first performed on a “stan-
dard” column used for detailed essential oil
profiling (60 m × 0.25 mm i.d. × 1 µm MeSi).
The operational conditions optimized for rou-
tine QC were applied. Secondly, the analyses
were repeated on a 20 m × 0.1 mm i.d. × 0.4 µm
MeSi. The operational conditions for the nar-
rowbore column were calculated by using the
method-translation software. The most impor-
tant operational conditions are summarized in
Table 6. From the method-translation software
program, a speed gain factor of 5.9 is predicted.
Note that the carrier gas in the analyses are he-
lium and hydrogen for the 0.25 mm i.d. and the
0.1 mm i.d. columns, respectively.
The chromatograms obtained on the respec-
tive columns are compared in Figure 64 top (nut-
meg oil, standard column) and bottom (nut-
meg oil, narrow bore column). From these chro-
matograms, it is obvious that the resolution is
exactly the same on both columns. The analy-
sis on the narrowbore column is much faster.
For the last-eluting peak, a speed gain factor of
5.7 is measured, which is close to the predicted
speed gain of 5.9. Since for the calculation, the
nominal column lengths were used, it might be
expected that the correlation could be even bet-
ter if actual column lengths are measured and
used in the method-translation software.
10.2. The Concept of Retention Time
Locking
Recent developments in capillary GC, i.e., elec-
tronic pneumatic control (EPC) of the carrier
Gas Chromatography 59
gas, improved oven temperature stability, and
excellent reproducibility in column making have
led to the concept of retention time locking
(RTL) [77], [78]. With retention time locked data
bases, absolute retention times instead of reten-
tion indices can be used to elucidate the struc-
tures of eluting solutes. Moreover, retention time
locking can be used in combination with dif-
ferent injectors and detectors. Exact scaling of
capillary GC – FID, capillary GC – MS, and cap-
illary GC – AED chromatograms is feasible.
The concept is illustrated with the analysis
of some organochlorine pesticides in wine. Fig-
ure 65 shows the capillary GC – AED trace in the
chlorine emission line (837 nm) of a wine ex-
tract. RTL conditions were adapted to the anal-
ysis, and the identities were searched via a pes-
ticide RTL database. A retention time window
of 0.5 (± 0.25 min from the measured retention
time) and the presence of chloor were introduced
in the RTL dialogue box. From the search for
the main peak eluting at 21.93 min (Table 7) it is
clear that the smallest deviation is obtained for
procymidone. The presence of this compound
was confirmed by using RTL conditions in cap-
illary GC – MS. The other chlorine compounds,
detected by capillary GC – AED analysis, could
not be identified directly by capillary GC – MS.
Owing to the complexity of the chromatogram
no clear spectra were obtained. For these com-
pounds, the result screener was used. Hereby,
the TIC is searched for specific ions for all pes-
ticides present in the database (567 pesticides)
in their elution window. The peak at 25.64 min
in the AED trace was identified as p,p -DDD.
The peak at 28.40 min was identified as iprodi-
one. The peak at 29.76 min could not be identi-
fied since no ions corresponding to a pesticide
present in the database and eluting in this time
window could be detected.
60 Gas Chromatography
Table 6. Experimental conditions for essential oil analysis on a conventional and on a narrowbore column. The conditions in italics for the
narrowbore column were calculated by the method-translation software. The standard operating conditions (SOP) on the conventional column
apply broader conditions than needed for the essential oil analysed here.

Column 60 m × 0.25 mm i.d. × 1 µm HP-1 20 m × 0.1 mm i.d. × 0.4 µm HP-1

Injection split, 1 µL, 1/50 split ratio, 250 ◦ C split, 1 µL, 1/500 split ratio, 250 ◦ C
Carrier type helium hydrogen
Carrier pressure 209 kPa, constant pressure 411 kPa, constant pressure
Carrier flow 1.74 mL/min at 50 ◦ C 0.87 mL/min at 50 ◦ C
Velocity 29.5 cm/s (average at 50 ◦ C) 58 cm/s (average at 50 ◦ C)
Hold-up time 3.39 min 0.57 min
Oven program 50 ◦ C – 2 ◦ C/min – 275 ◦ C – 40 min 50 ◦ C – 11.88 ◦ C/min – 275 ◦ C – 7 min
Detection FID FID
Signal data rate 10 Hz 50 Hz
Analysis time 152.5 min 25.94 min

Figure 64. Analyses of nutmeg oil on a 60 m × 0.25 mm i.d. × 1 µm MeSi column (top trace) and on a 20 m × 0.1 mm × 0.4 µm
MeSi column (bottom trace)

Figure 65. Capillary GC – AED chromatogram at the 837 nm emission line of a white wine extract recorded under RTL
conditions
This example clearly demonstrates the com-
plementary nature of capillary GC – AED and
capillary GC – MS. The selectivity of the AED
results in simple profiles and allows fast screen-
ing of pesticides in samples. Capillary GC – MS
in combination with the result screener allows
confirmation of the detected solutes. Analysis
of the samples with capillary GC – MS only re-
sults in complex chromatograms and more time
consuming data interpretation is needed. Reten-
tion time locking also allows the correct match-
ing of the capillary GC – AED chromatograms
with the capillary GC – MS chromatograms. The
corresponding peaks elute at virtually the same
retention times.
10.3. Towards Black Boxes
State-of-the-art GC offers column efficiencies
ranging from 5000 to 500 000 plates (packed
or short megabore columns to long narrowbore
columns), with sample capacities from micro-
gram to subnanogram amounts. Selectivity can
be introduced in all parts of the GC system. Col-
umn selectivity can be adapted to the specific
need by selecting the most suitable stationary
phase. To enhance resolution of critical pairs,
column selectivity can be optimized by selectiv-
ity tuning between two columns coated with dif-
ferent stationary phases or by two-dimensional
CGC. Multidimensional CGC, HPLC – CGC,
SFE – CGC, etc., provide preseparation and en-
richment of relevant fractions. In addition to
universal inlets a number of selective inlets are
Gas Chromatography 61
available in GC. GC enjoys universal detec-
tion and sensitive, selective detection. Selec-
tive recognition can be performed routinely by
CGC – mass spectroscopy, CGC – Fourier trans-
form infrared spectroscopy, and CGC – atomic
emission detection, to provide sensitive and se-
lective quantitation of target compounds and
structural elucidation or identification of un-
knowns.
There is much more to come, such as compre-
hensive capillary GC, hyphenation with time-of-
flight MS (capillary GC – TOFMS) and induc-
tively coupled plasma MS (capillary GC – ICP-
MS) . . . to mention a few recent technological
realizations.
Nothwithstanding all these capabilities of
GC, the data are often disappointing, as evi-
denced by results from round-robin tests. Devi-
ations can be as high as 100 ppm for BTX mea-
surements in air in the 100 ppm level, as high
as 30 ppb for trihalomethanes at the 50 ppb level
in drinking water, as high as 60 ppt (ppt = 1 part
in 1012 ) for organochloropesticides in the 70 ppt
level in wastewater, etc. How should data such
as 3.34 ppt 2,3,7,8 TCDD be interpreted?
What are the reasons for this? Two main as-
pects can be identified. First of all, there is an ed-
ucational problem. Technicians in the laboratory
often lack experience and expertise, and more-
over time and money for training are unavail-
able. On the other hand, shift of good staff
now occurs very quickly without time to trans-
fer the know-how. The second aspect is precol-
umn errors (e.g., sample introduction and sam-
ple preparation), and both parts of the total ana-
62 Gas Chromatography
Table 7. Results of retention time locked pesticide data base search

Search results for 21.939 +/− 0.250 min

Contains elements: Cl
Does not contain elements: {no restriction}
RTT file searched: C:\\HPCHEM\\RTL\\HPGCPST.RTT
FID RT Compound name MW Formula ∆ RT (min)
21.825 Chlorbenside 269.19 C:13,H:10,Cl:2,S:1, − 0.114
21.971 Procymidone 284.14 C:13,H:11,Cl:2,N:1,O:2, + 0.032
22.037 trans-Chlordane 409.78 C:10,1,Cl:6,H:8, + 0.098
22.95 Chlorflurecol-Me- ester 274.70 C:15,H:11,Cl:1,O:3, + 0.156

Search results for 25.649 +/− 0.250 min

Contains elements: Cl
Does not contain elements: {no restriction}
RTT file searched: C:\\HPCHEM\\RTL\\HPGCPST.RTT
FID RT Compound name MW Formula ∆ RT (min)
25.409 Chlorobenzilate 325.19 C:16,H:14,Cl:2,O:3, − 0.240
25.434 Chloropropylate 339.22 C:17,H:16,Cl:2,O:3, − 0.215
25.581 Diniconazole 326.23 C:15,H:17,Cl:2,N:3,O:1, − 0.068
25.654 Cyprofuram 279.72 C:14,H:14,Cl:1,N:1,O:3, + 0.005
25.703 p,p -DDD 320.05 C:14,H:10,Cl:4, + 0.054
25.763 Etaconazole 328.20 C:14,H:15,Cl:2,N:3,O:2, + 0.114

25.786 o,p -DDT 354.49 C:14,H:9,Cl:5, + 0.137
25.823 Flamprop-isopropyl 363.82 C:19,H:19,Cl:1,F:1,N:1,O:3, + 0.174

Search results for 28.404 +/− 0.250 min

Contains elements: Cl
Does not contain elements: {no restriction}
RTT file searched: C:\\HPCHEM\\RTL\\HPGCPST.RTT
FID RT Compound name MW Formula ∆ RT (min)
28.239 Endrin ketone 380.91 C:12,H:8,Cl:6,O:1, − 0.165
28.362 Benzoylprop ethyl 366.24 C:18,H:17,Cl:2,N:1,O:3, − 0.042
28.424 Iprodione 330.17 C:13,H:13,Cl:2,N:3,O:3, + 0.020
28.436 Dichlorophen 269.13 C:13,H:10,Cl:2,O:2, + 0.032
28.545 Leptophos oxon 396.00 C:13,H:10,Br:1,Cl:2,O:3,P:1, + 0.141
28.572 Chlorthiophos sulfoxide 377.24 C:11,H:15,Cl:2,O:4,P:1,S:2, + 0.188

Search results for 29.768 +/− 0.250 min

Contains elements: Cl
Does not contain elements: {no restriction}
RTT file searched: C:\\HPCHEM\\RTL\\HPGCPST.RTT
FID RT Compound name MW Formula ∆ RT (min)
29.699 Phosalone 367.80 C:12,H:15,Cl:1,N:1,O:4,P:1,S:2, − 0.069
29.754 Leptophos 412.06 C:13,H:10,Br:1,Cl:2,O:2,P:1,S:1, − 0.014
29.848 Mirex 545.55 C:10,Cl:12, + 0.080

lytical procedure are interrelated. Future devel- 11. References

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 Gas Production 1

Gas Production
Heinz Hiller, Lurgi, Frankfurt am Main, Germany (Chap. 1)
Rainer Reimert, (formerly Lurgi) Engler-Bunte-Institut der Universität Karlsruhe, Karlsruhe, Germany
(Chap. 1, 4 and 7.3)
Friedemann Marschner, Lurgi, Frankfurt am Main, Germany (Chap. 2)
Hans-Joachim Renner, Lurgi, Frankfurt am Main, Germany (Chap. 2)
Walter Boll, Lurgi, Frankfurt am Main, Germany (Chap. 2 and 5.3)
Emil Supp, Lurgi, Frankfurt am Main, Germany (Chap. 3, 5.1 and 5.2)
Miron Brejc, Lurgi, Frankfurt am Main, Germany (Chap. 3)
Waldemar Liebner, Lurgi, Frankfurt am Main, Germany (Chap. 3)
Georg Schaub, (formerly Lurgi) Engler-Bunte-Institut der Universität Karlsruhe, Karlsruhe, Germany
(Chap. 4)
Gerhard Hochgesand, Lurgi, Frankfurt am Main, Germany (Chap. 5 and 6.3)
Christopher Higman, Lurgi, Frankfurt am Main, Germany (Chap. 5.1, 5.2 and 7.2)
Peter Kalteier, Lurgi, Frankfurt am Main, Germany (Chap. 5.1 and 5.2)
Wolf-Dieter Müller, Lurgi, Frankfurt am Main, Germany (Chap. 5.3)
Manfred Kriebel, Lurgi, Frankfurt am Main, Germany (Chap. 5.4)
Holger Schlichting, Lurgi, Frankfurt am Main, Germany (Chap. 5.4)
Heiner Tanz, (formerly Lurgi, Frankfurt), IVTP, Dreieich, Germany (Chap. 5.5, 5.6, 5.7 and 5.8)
Hans-Martin Stönner, Lurgi, Frankfurt am Main, Germany (Chap. 1.5, 6.1 and 6.2)
Helmut Klein, Lurgi, Frankfurt am Main, Germany (Chap. 6.2)
Wolfgang Hilsebein, Lurgi, Frankfurt am Main, Germany (Chap. 7.1)
Veronika Gronemann, Lurgi, Frankfurt am Main, Germany (Chap. 7.1)
Uwe Zwiefelhofer, Lurgi, Frankfurt am Main, Germany (Chap. 7.2)
Johannes Albrecht, Lurgi, Frankfurt am Main, Germany (Chap. 7.3)
Christopher J. Cowper, British Gas, London, United Kingdom (Chap. 8)
Hans Erhard Driesen, Engler-Bunte-Institut der Universität Karlsruhe, Karlsruhe, Germany (Chap. 8)

Related Articles → Coal Liquefaction and → Coal Pyrolysis are separate keywords.

1. Introduction . . . . . . . . . . . . . . 3 1.4. Characteristics of the Basic

1.1. Types of Gases; General Overview Processes . . . . . . . . . . . . . . . . 16
of Production Methods 1.5. Product Gas Treatment . . . . . . . 18
and Characteristics . . . . . . . . . 3 1.5.1. Purification Processes . . . . . . . . . 18
1.1.1. Water Gas and Producer Gas . . . . 3 1.5.2. Conditioning . . . . . . . . . . . . . . 19
1.1.2. Synthesis Gas and Reduction Gas . 4
1.5.3. Byproducts . . . . . . . . . . . . . . . 20
1.1.3. Town Gas and Medium-Btu Gas . . 7
1.1.4. Biogas and Landfill Gas . . . . . . . 9 2. Steam Reforming of Natural Gas
1.1.5. Rich Gas and Substitute Natural Gas and Other Hydrocarbons . . . . . 21
(SNG) . . . . . . . . . . . . . . . . . . 9 2.1. Feedstocks . . . . . . . . . . . . . . . 21
1.2. Raw Materials for Gasification . . 9 2.2. Natural Gas and Other Gaseous
1.3. Physicochemical Basis for Hydrocarbons . . . . . . . . . . . . . 22
Gas Production . . . . . . . . . . . . 12 2.2.1. Principles . . . . . . . . . . . . . . . . 24

c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 169.pub2
2 Gas Production

2.2.2. Catalysts, Catalyst Poisons, 5.1. Carbon Monoxide Shift

Desulfurization . . . . . . . . . . . . . 26 Conversion . . . . . . . . . . . . . . . 77
2.2.3. Tubular Reformers . . . . . . . . . . . 27 5.1.1. Fundamentals . . . . . . . . . . . . . . 77
2.2.4. Production of Fuel Gas and 5.1.2. Catalysts . . . . . . . . . . . . . . . . . 78
Synthesis Gas . . . . . . . . . . . . . . 29 5.1.3. Clean Gas Shift Conversion . . . . . 79
2.2.5. Special Reforming Processes . . . . 30 5.1.4. Raw Gas Conversion . . . . . . . . . 81
2.3. Tubular Steam Reforming of 5.1.5. General Comments on Reactor
Liquid Hydrocarbons . . . . . . . . 31 Arrangements . . . . . . . . . . . . . . 82
2.3.1. Commercial Processes . . . . . . . . 32 5.1.6. Noncatalytic Quench Conversion . 82
2.3.2. Fuel Gas and Synthesis Gas from 5.2. Carbonyl Sulfide Conversion . . . 82
Liquid Hydrocarbons . . . . . . . . . 32 5.3. Methanation and Methane
2.3.3. Special Processes . . . . . . . . . . . 32 Synthesis . . . . . . . . . . . . . . . . 83
2.4. Prereforming . . . . . . . . . . . . . 33 5.3.1. Definitions and Applications . . . . 83
2.4.1. Principles . . . . . . . . . . . . . . . . 33 5.3.2. Principles of Methanation . . . . . . 84
2.4.2. Catalysts . . . . . . . . . . . . . . . . . 34 5.3.3. Methanation as a Step in Hydrogen
2.4.3. Prereforming of Natural Gas . . . . 34 Purification . . . . . . . . . . . . . . . 85
2.4.4. Prereforming of Naphtha; 5.3.4. Methanation of Rich Gas . . . . . . . 86
Rich Gas Process . . . . . . . . . . . 35 5.3.5. Methane Synthesis from Gases with
2.5. Autothermal Catalytic Reforming 37 High Carbon Monoxide Content . . 86
3. Noncatalytic Partial Oxidation 5.4. Absorption Processes . . . . . . . . 90
and Special Gasification Processes 5.4.1. General . . . . . . . . . . . . . . . . . . 90
for Higher-Boiling Hydrocarbons 40 5.4.2. Processes for Carbon Dioxide and
3.1. Raw Materials . . . . . . . . . . . . . 40 Sulfur Compound Absorption . . . 93
5.4.2.1. Physical Absorption Processes . . . 94
3.2. Partial Oxidation of
5.4.2.2. Chemical Absorption Processes . . 101
Hydrocarbons . . . . . . . . . . . . . 42
5.4.2.3. Physical – Chemical Absorption
3.2.1. Principle . . . . . . . . . . . . . . . . . 42
Processes . . . . . . . . . . . . . . . . 107
3.2.2. Types of Processes . . . . . . . . . . . 43
5.4.2.4. Comparison of Various Absorption
3.2.3. Influencing Raw Gas Composition . 47
Processes for Hydrogen Production
3.2.4. Submerged Flame Process . . . . . . 51
and IGCC . . . . . . . . . . . . . . . . 108
3.3. Hydrogenating Gasification . . . . 51 5.4.3. Liquid-Phase Oxidation Processes . 112
4. Gas Production from Coal, Wood, 5.4.4. Removal of Gas Impurities of Low
and Other Solid Feedstocks . . . . 52 Concentration . . . . . . . . . . . . . . 116
4.1. Fundamentals . . . . . . . . . . . . . 53 5.5. Adsorption Processes . . . . . . . . 118
4.1.1. Thermodynamics of Chemical 5.5.1. Fundamentals . . . . . . . . . . . . . 118
Reactions . . . . . . . . . . . . . . . . 53 5.5.2. The “Classic” Method . . . . . . . . 120
4.1.2. Kinetics . . . . . . . . . . . . . . . . . 54 5.5.3. Pressure-Swing Adsorption . . . . . 121
4.2. Classification and General 5.5.4. Adsorption on Activated Carbon . . 122
Characteristics of Gasification 5.6. Cryogenic Processes . . . . . . . . 122
Processes . . . . . . . . . . . . . . . . 56 5.6.1. Partial Condensation . . . . . . . . . 123
4.2.1. Criteria for Classification . . . . . . 56 5.6.2. Liquid Methane Wash Process . . . 124
4.2.2. Criteria for Process Assessment . . 57 5.6.3. Liquid Nitrogen Wash Process . . . 125
4.2.3. Mathematical Modeling of 5.7. Gas Separation by Membranes . 126
Gasification Reactors . . . . . . . . . 57 5.8. Addition of Inerts or Other
4.3. Characterization of Solid Substances . . . . . . . . . . . . . . . 127
Feedstocks for Gasification . . . . 59 6. Handling of Byproducts . . . . . . 128
4.4. Moving- or Fixed-Bed Processes . 62 6.1. Aqueous Condensates . . . . . . . . 128
4.5. Fluidized-Bed Processes . . . . . . 66 6.1.1. Mechanical Treatment . . . . . . . . 129
4.6. Entrained-Flow Processes . . . . . 70 6.1.2. Extraction and Adsorption of
4.7. Molten-Bath Processes . . . . . . . 72 Organic Substances . . . . . . . . . . 131
4.8. Underground Coal Gasification . 74 6.1.3. Removal and Recovery of Ammonia
4.9. Environmental Aspects of and Sulfur . . . . . . . . . . . . . . . . 132
Gasification . . . . . . . . . . . . . . 75 6.1.4. Biological and Final Treatment . . . 134
5. Gas Treating . . . . . . . . . . . . . . 76 6.1.5. Removal of Heavy Metals . . . . . . 135
 Gas Production 3

6.1.6. Example of an Industrial 7.3.3. Installations and Design Studies . . 150

Application . . . . . . . . . . . . . . . 135 8. Analysis and Quality Control . . . 152
6.2. Hydrocarbon Condensates . . . . 136 8.1. Quality Specifications . . . . . . . . 152
6.2.1. Distillation . . . . . . . . . . . . . . . 137 8.1.1. Combustion Characteristics . . . . . 153
6.2.2. Hydrorefining . . . . . . . . . . . . . . 137 8.1.2. Minor Constituents . . . . . . . . . . 153
6.3. Gaseous Byproducts . . . . . . . . . 139 8.2. Test Methods . . . . . . . . . . . . . 153
7. Typical Examples of Complex Gas 8.2.1. Determination of Combustion
Production Plants . . . . . . . . . . 141 Characteristics . . . . . . . . . . . . . 153
7.1. Methanol Production from 8.2.1.1. Calorimetry . . . . . . . . . . . . . . . 153
Natural Gas . . . . . . . . . . . . . . 141
8.2.1.2. Density . . . . . . . . . . . . . . . . . . 154
7.1.1. Methanol Production Based on
8.2.1.3. Wobbe Index . . . . . . . . . . . . . . 154
Catalytic Autothermal Reforming . 142
8.2.2. Analytical Methods . . . . . . . . . . 155
7.1.2. Comparison of Conventional Steam
8.2.2.1. General Methods for Determination
Reforming and Combined
of Several Components . . . . . . . . 155
Reforming Processes for
Methanol Production . . . . . . . . . 143 8.2.2.2. Specific Methods for Determination
7.2. Hydrogen Production Based on of Individual Components . . . . . . 155
Heavy Residues . . . . . . . . . . . . 143 8.2.2.3. Methods for Determination of Minor
7.3. Combined Cycle Power System Components . . . . . . . . . . . . . . . 156
Based on Coal . . . . . . . . . . . . . 147 8.2.2.4. Determination of Trace Constituents 158
7.3.1. Introduction . . . . . . . . . . . . . . . 147 9. Acknowledgement . . . . . . . . . . 158
7.3.2. Fundamentals . . . . . . . . . . . . . . 148 10. References . . . . . . . . . . . . . . . 158

1. Introduction used as a fuel gas, e.g., in gas turbines (see Sec-

1.1. Types of Gases; General Overview
of Production Methods and
Characteristics
Gases for industrial or heating uses can be classi-
fied in various ways. The most appropriate clas-
sification appears by calorific (heating) value
ranges, in kJ/m3 (STP):
Water and producer gas 4600 – 12 500
Synthesis and reduction gas ca. 12 500
Town gas and medium-Btu gas 16 700 – 20 000
Biogas and landfill gas 18 000 – 29 000
High-Btu gas and substitute natural gas (SNG) 25 000 – 37 000
A distinction has deliberately been made bet-
ween water gas and synthesis gas, although wa-
ter gas was formerly used in large quantities for
synthesis as well. However, the so-called water
gases are based on very specific raw materials
and belong to a different generation of produc-
tion methods compared to ynthesis gases pro-
duced in modern plants. Reduction gas refers to
gases used in iron production.
Synthesis gas is the basis for most of the hy-
drogen (→ Hydrogen) produced, and it is also
tion 7.3).
Biogas and landfill gas (→ Methane) are pro-
duced during biological degradation of organic
matter. They may be collected and purified ei-
ther to be used further (renewable energy) or to
prevent air pollution.
1.1.1. Water Gas and Producer Gas
The terms water gas and producer gas were first
used in solid fuel gasification technology. Both
types of gas were very important from the 1920s
to the 1940s. They were the basis for producing
synthesis gas, town gas, and fuel gas. The tech-
nology is of only minor importance today be-
cause the raw material basis has shifted largely
from solid fuels to liquid and gaseous fuels, and
high-performance processes have been devel-
oped for coal-based synthesis gas, town gas, and
grid gas.
Production of Water Gas. Water gas is usu-
ally produced in an alternating operation, i.e.,
by alternately hot blowing a fuel layer with air
and gasifying it with steam. Among its vari-
ous modifications, the production of so-called
blue water gas from coke was the most common
method, yielding gas with high hydrogen and
4 Gas Production
carbon monoxide contents which was suitable
for use as synthesis gas. By addition of higher
hydrocarbons, the calorific value of water gas
could be increased (carbureting) so it could be
used as town gas.
Although most water gas plants were based
on coke, plants also operated with anthracite and
noncaking highly volatile types of coal (coal wa-
ter gas or double gas). Coal with a high volatile
matter content gives gases with higher calorific
values because gasification gas is supplemented
by a considerable amount of devolatilization gas.
In the water gas process with its cyclic mode
of operation, coke has two functions: (1) it re-
acts with blowing air during warm-up and with
steam during gasification, and (2) serves as a
heat regenerator.
Because of the expensive raw material (coke),
complicated batch operation, and relatively low
output per gasifier (6000 – 9000 m3 (STP)/h),
this method of producing synthesis and town
gases has been replaced by more up-to-date
processes. The gas production of synthesis gas
plants based on either natural gas (in tubular re-
formers; see Chap. 2) or heavy oil (by partial
oxidation; see Chap. 3), and of modern coal
gasification plants (see Chap. 4) is ten times
higher than that of water gas plants.
Production of Producer Gas. Producer gas
is obtained by supplying a gasification agent
consisting of air and steam continuously, rather
than cyclically, to a gas producer of the same
general design as a water gas producer. This gas
has a lower calorific value than water gas be-
cause it contains atmospheric nitrogen. Producer
gas was obtained from a variety of rotary grate
gas producers from the 1920s to the 1940s. Be-
cause of its high nitrogen content, which cannot
be eliminated at economically justifiable cost,
this gas is not suitable for use as synthesis gas;
it was employed almost exclusively as fuel gas
and as an additive to town gases in municipal
works.
In addition to coke, noncaking coals were
also used as feedstocks, and a few plants were
also built for the gasification of caking bitumi-
nous coals under atmospheric conditions and un-
der pressure (Lurgi pressure gasification).
Nature of Water Gas and Producer Gas.
The following is a typical analysis of a water
gas, in percent by volume:
Carbon dioxide 5 Hydrogen 50
Carbon monoxide 40 Nitrogen 5
A typical analysis of a producer gas, in per-
cent by volume, is
Carbon dioxide 5.5 Hydrogen 10.5
Carbon monoxide 29.0 Nitrogen 55.0
The higher heating values (HHV) for wa-
ter gas based on coke and for producer gas are
10 500 – 12 500 kJ/m3 (STP) and 4600 – 6700
kJ/m3 (STP), respectively.
The nitrogen content of water gas, amount-
ing to ca. 5 vol %, does not originate from coke
or coal for the most part, but is due to the fact
that air remains in the coke pores on transition
from the blowing to the gasification period. This
nitrogen content can be lowered by discarding a
small fraction of the gas produced at the begin-
ning of the gasification period.
1.1.2. Synthesis Gas and Reduction Gas
The gas production method used depends on the
raw materials. The raw materials are mainly nat-
ural gas, naphtha, heavy vacuum residue, and
coal (see Chaps. 2, 3, 4). In addition, uncon-
ventional fuels such as solid or liquid waste
materials or biomass gain interest. However, in
the recent decades most of the world produc-
tion of synthesis gas was based on natural gas
and sulfur-rich heavy vacuum residues. Because
of more stringent environmental protection re-
quirements, these residues may no longer be
burned in boiler plants in many countries, so
their market value is often low. Countries that
do not have these two raw materials, particu-
larly countries in which no natural gas is avail-
able, often use naphtha. Depending on certain
boundary conditions such as the relationship bet-
ween oil and coal prices, as well as local fac-
tors and strategic considerations, plants based
on coal will continue to be built.
Production of Synthesis Gas. Because syn-
thesis gas is processed under elevated pressure,
a trend toward operating gas production plants
at increasingly high pressure could be observed.
Gas production at higher pressure reduces the

cost of compressing synthesis gas to the required
synthesis pressure.
Natural Gas as Raw Material (Chap. 2).
Synthesis gases are produced from natural gas
mainly in tubular reformers. If the atural gas
contains virtually no nitrogen, a temperature
of 750 – 800 ◦ C is sufficient for gas suitable in
ammonia synthesis. Residual unreacted methane
is reformed in a secondary reformer (catalytic
partial oxidation with air) with simultaneous
adjustment of its nitrogen content.
For normal methanol synthesis, reforming is
performed in one step in a tubular reactor at 850
– 900 ◦ C in order to leave as little methane as
possible in the synthesis gas.
For large methanol synthesis plants, Lurgi
has introduced a two-step combination that gives
better results. In the primary tubular reformer,
lower temperature (ca. 800 ◦ C) but higher pres-
sure (2.5 – 4.0 MPa instead of 1.5 – 2.5 MPa)
are applied. The secondary reformer operates
with a fixed catalyst bed as in the case of am-
monia synthesis gas, but pure oxygen is used for
partial oxidation.
More recently, Lurgi developed another two-
step gas production scheme. It is based on cat-
alytic autothermal reforming with an adiabatic
prereformer and has economical advantages for
very large methanol plants (Section 7.1).
The various tubular reformer designs differ
primarily in the method of firing the catalyst-
containing tubes (from the side or top, terraced,
or from the bottom). Subsequent developments
of combined reforming resulted in the integra-
tion of the primary and the secondary reform-
ing step in one apparatus using the thermal en-
ergy of the effluent of the autothermal process
for heating the steam reformer part (M.W. Kel-
logg, Uhde). Exxon tested the simultaneous re-
forming and partial oxidation of natural gas in a
reactor with fluidized catalyst. Apart from tubu-
lar reformer technology with or without a sec-
ondary reformer, partial oxidation (in one step)
is still used sporadically for reforming natural
gas. This can be performed either noncatalyt-
ically (Shell, Texaco) or catalytically (Lurgi).
The latter is used especially when low ratios of
hydrogen to carbon monoxide are required.
Naphtha as Raw Material (Chap. 2). The
purity of naphtha allows the use of catalysts.
Therefore, the production of synthesis and re-
duction gases from naphtha is carried out almost
Gas Production 5
exclusively catalytically and at elevated pres-
sure.
Externally heated tubular reformers con-
taining special catalysts are used to produce
hydrogen-rich gases (e.g., ammonia synthesis).
Two processes stand out from the others: they
differ in the types of tubular reformers recom-
mended and, primarily, in the type of nickel cat-
alyst used. Topsøe uses a nickel catalyst without
alkali; ICI employs one with a definite alkali
content.
In future naphtha might replace methanol as
a raw material for hydrogen produced on board
of vehicles driven by fuel cells. Due to the much
smaller size of such production units as com-
pared with plants in the petrochemical industry
and due to restrictions by volume and by utilities
(e.g., steam and water), the production scheme
and above all the reactors and heat exchangers
for naphtha reforming in vehicles look rather dif-
ferent.
Apart from single-stage tubular reforming,
two-stage processes have also proved success-
ful for the production of gases rich in carbon
monoxide, such as those required for methanol
and oxo synthesis. An example of a two-stage
process is the Recatro process, developed by
BASF – Lurgi. Here, naphtha is converted with
relatively little steam in an initial low-temper-
ature adiabatic stage over a special nickel cat-
alyst to produce a rich gas containing ca. 60
– 65 vol % methane plus hydrogen and carbon
dioxide. This gas is supplied together with the
remaining steam to a conventional tubular re-
former to be reformed to carbon monoxide-rich
synthesis gas in the presence of a conventional
catalyst. The two-stage operation makes carbon
dioxide recycling unnecessary in many cases or
reduces it considerably.
A few plants using partial oxidation with
(Lurgi) or without (Shell, Texaco) catalysts have
been built.
Heavy Fuel or Residual Oil as Raw Material
(Chap. 2). For the production of synthesis and
reduction gases from heavy and residual oils,
two processes are accepted worldwide: the Shell
and the Texaco process, both operating under
elevated pressure and noncatalytic. The Texaco
process was originally designed for partial ox-
idation of natural gas; the Shell process, devel-
oped later, was tailored from the beginning to
gasification of heavy oil. The differences bet-
6 Gas Production
ween the two processes are virtually negligible
and involve only details of equipment design.
Coal as Raw Material (Chap. 4). Processes
employing coal that are used in practice oper-
ate on a noncatalytic basis. Various processes
operating under elevated pressure are available:
Lurgi, BGL (British Gas/Lurgi), HTW (High
Temperature Winkler), U-Gas, Texaco, Shell
and Prenflo. The Koppers – Totzek process and
the original Winkler process operate at atmo-
spheric pressure. Coal gasification plants for the
production of synthesis gas built since the 1950s
are based essentially on the Koppers or Lurgi
processes.
In view of the distribution of fossil fuels in the
world — almost ten times as much coal exists as
petroleum and natural gas, and it is distributed
relatively uniformly — and the sharp increase in
oil prices in the 1970s, efforts have been made
in many countries to develop new coal gasifi-
cation processes tailored to the requirements of
particular countries and their coal deposits.
In most processes, the heat required for gasifi-
cation is provided by partial oxidation with pure
oxygen. These processes are based essentially
on the following three process arrangements:
1) moving bed,
2) one or more fluidized beds, and
3) entrained-flow systems in which coal dust
and the gasification agent are conveyed cocur-
rently.
Combinations of these three process arrange-
ments are being investigated, as are processes
applying high-temperature melts.
The overall arrangement of various coal gasi-
fication plants, including downstream units, is
determined essentially by the composition of
the raw gases. The gases produced at increased
pressure by the Lurgi and by the BGL gasi-
fication processes contain methane, which can
be converted to carbon monoxide and hydrogen
for downstream ammonia or methanol synthe-
sis, or can be removed before entering the high-
pressure compressor. The Koppers – Totzek, the
Texaco, as well as the other entrained-flow pro-
cesses yield a gas without methane, but with
a higher specific oxygen consumption. As in
all high-temperature gasification processes, gas
from the latter two processes has a high car-
bon monoxide content, requiring considerable
conversion measures for certain syntheses. The
gasification processes applied to coal are also
suitable for petrol coke if they can cope with its
low reactivity and they are also applied when
biomass or waste materials are used as fuels.
Production of Reduction Gas. In principle,
reduction gas production is very similar to that
of synthesis gas. However, iron ore is usually
reduced under atmospheric conditions, so re-
duction gas can be produced at atmospheric
or slightly increased pressure. Reduction gases
used for the production of sponge iron by various
direct reduction processes (→ Iron, Chap. 2.6)
must meet certain requirements. Generally, the
proportion of oxidizing components such as
steam and carbon dioxide in the gas mixture pro-
duced should be as low as possible, always <
10 %. This goal can be achieved by cooling the
gases produced from coal, oil, naphtha, or natu-
ral gas and removing carbon dioxide. However,
because reduction gases in the shaft furnaces
of steel works are needed at high temperature,
more cost-effective solutions are being sought
and used. In the Midrex process natural gas is
converted at ca. 1000 ◦ C in the tubular reformer,
without the addition of steam, thereby producing
only hydrogen and carbon monoxide; the con-
version is such that the reformed gases can be
used directly in the shaft furnace.
As the recovery of byproducts from coke
oven raw gas (benzene, phenol) loses economi-
cal attractiveness, reduction gas is considered to
be produced from coke oven raw gas by catalytic
partial oxidation.
Composition and Aftertreatment. Synthe-
sis gas requirements depend on the intended ap-
plication.
Ammonia synthesis units now generally op-
erate between 13.0 and 22.0 MPa and require
gas with a hydrogen: nitrogen ratio of 3: 1. Im-
purities are limited in modern processes to < 1
ppm for sulfur and 2 – 10 ppm for oxygen-con-
taining components such as oxygen itself, car-
bon dioxide, and water. With a view to the econ-
omy of synthesis (i.e., the purge gas quantities
to be branched off), the methane content of syn-
thesis gas must not exceed 0.5 – 0.8 vol %.
This means that the reformer and gasifica-
tion gases produced from various raw materials
must be conditioned appropriately. If the meth-
ane content is originally considerably high it can
 Gas Production 7

be lowered by secondary reforming with oxygen of Comox and Nimox catalysts, and subsequent
or air. Because all reformed gases contain carbon adsorption prior to the reforming of naphtha and
monoxide, they have to be converted, irrespec- natural gas in the tubular reformer).
tive of the raw materials from which they are pro- Purities applicable in methanol synthesis are
duced; this is done by catalytically reacting car- also required for oxo synthesis. However, be-
bon monoxide with steam to form hydrogen and cause the latter often requires a hydrogen: car-
carbon dioxide (shift conversion). Depending on bon monoxide ratio of ca. 1: 1, the carbon: hy-
its residual content after shift conversion, either drogen ratio of the feedstock may require that
the carbon monoxide concentration must be low- carbon dioxide be recycled or fed to the gasifi-
ered (to the ppm range) in a methanation stage cation unit.
or it must be removed at low temperatures by a For iron ore reduction gas, the sulfur content
liquid nitrogen wash. Hydrogen sulfide, organic must be reduced to a few parts per million. Table
sulfur compounds, and carbon dioxide have to 1 shows typical analysis data for raw gases from
be removed by appropriate washing procedures. various starting materials.
Similar conditioning and purification pro-
cesses have to be applied for the production of Table 1. Typical raw gas analyses
hydrogen for fuel cells (→ Fuel Cells).
Feedstocks and processes Content, vol %
Methanol is generated from carbon monox-
H2 CO CH4 C2+ N2 + CO2 H2 S +
ide as well as from carbon dioxide: Ar COS
Coal
2 H2 +CO
CH3 OH
Lurgi pressure 43 12 11.5 1 0.3 32 0.2
gasification
3 H2 +CO2
CH3 OH+H2 O BGL 28 57 7.1 0.4 4.2 3 0.3
Koppers – Totzek 30 55 0.1 1.4 13.2 0.3
The preferred reaction path goes via Texaco 37 41.3 0.1 0.6 20.7 0.3
carbon monoxide, some carbon dioxide Oil gasification
is required for kinetic reasons. The ratio Shell – Texaco 46 47 0.5 0.6 5.5 0.4
Naphtha
(cH2 − cCO2 )/(cCO + cCO2 ) should generally Tubular reformer 67 19 3 11
be between 2.0 and 2.2. The theoretical value Recatro (BASF – 66 22 4 8
derived from adding both reaction equations Lurgi)
Natural gas
after pondering each of them arbitrarily is 2.0. Tubular reformer 73 16 4 7
A higher carbon monoxide content is required
for fuel methanol synthesis (Lurgi Octamix and
others), in which a mixture of methanol and 1.1.3. Town Gas and Medium-Btu Gas
higher alcohols is produced as an additive to mo-
tor fuel. For high-pressure methanol synthesis Because natural gas (→ Natural Gas) has be-
(35.0 MPa), which is still used in a few cases, the come the preferred fuel gas for households and
presence of methane adds an economic burden industry, the production of town and medium-
(as in ammonia synthesis). It is less important Btu gas from coal and liquid fuels is of minor
in low-pressure (5.0 – 10.0 MPa) methanol syn- importance today. High-temperature coking —
thesis (ICI, Lurgi) because compression costs formerly general practice in town gas works —
for this gas component are practically negligible has disappeared almost completely (→ Coal Py-
because of the lower compression ratio required. rolysis). The following is a brief outline of gasifi-
The content of sulfur compounds in the gas used cation processes for the production of town gas.
for low-pressure methanol synthesis, which is Basis of Production. When charcoal was re-
based on a special copper-containing catalyst, placed in the last century by coke from bitumi-
must be extremely low. The amount of hydro- nous coal to smelt iron in blast furnaces, large
gen sulfide and organic sulfur compounds in the quantities of degasification gas were produced
synthesis gas produced from raw materials with by the carbonization of caking coals. Initially,
relatively high sulfur content can be lowered to these gases were largely flared; later on, they
ca. 0.1 ppm by special processes (Rectisol for were distributed through piping systems supply-
coal and oil gasification gases; hydrogenation ing gas particularly to the municipalities in the
of the organic sulfur compounds in the presence
8 Gas Production
neighborhood of steelworks. The gas grids were
large enough to provide sufficient gas from the
coke ovens even at times of peak demand; on
Sundays and holidays, the gas was flared in the
coking plants.
With the increasing demand for grid gas, uti-
lization of the gas system improved, so that
towns had to build their own gas production fa-
cilities to meet peak requirements. These facil-
ities were based mainly on water gas, which in
some cases was carbureted.
Both solid and liquid or gaseous fuels were
used as raw materials for town gas production.
Liquid hydrocarbons such as fuel oil and, later
on, naphtha were preferred, but coal was also
used.
Plants using fuel oil are based mainly on a
cyclic process arrangement and became very
successful since the 1950s. Some of them use
straight thermal processes without catalysts, but
most employ a catalyst bed. During a blowing
phase, a bed of catalytic or noncatalytic material
is heated by the combustion of fuel oil with air.
After switching to the gasification period, fuel
oil is passed over the hot bed along with steam.
The ONIA GEGI and SEGAS processes and the
Koppers Cowper process have become widely
known [1].
The disadvantages of these cyclic processes
are their relatively low output and difficulties
caused by excessive wear of the switchover
mechanism. In addition, as environmental laws
tightened toward the end of the 1950s and be-
ginning of the 1960s, plant operators turned to
processes using lighter hydrocarbons and con-
tinuous operation. The development of special
catalysts (ICI, Topsøe) permitted gas production
from readily available liquid feedstocks (such as
lighter hydrocarbons and naphtha having a boil-
ing end point up to 200 ◦ C) to be carried out in
externally heated tubular reformers. Apart from
its higher efficiency, this mode of operation had
an additional advantage because the gases pro-
duced were available at increased pressure, thus
reducing the expenditure for their distribution
in pressure gas systems. The methane content of
the gases could be increased by keeping reac-
tion temperatures in the tubular reformer low, so
that after a cold carbureting stage with propane
– butane, standard town gas could be produced.
Cold carbureting was often not applicable be-
cause either propane – butane was not available
at a reasonable price, or certain standards with
respect to dew-point were not met, therefore,
modified processes aiming at increased produc-
tion of methane from naphtha (BASF/Lurgi,
British Gas, Japan Gasoline Corp.) were devel-
oped. Because methane content increases with
decreasing temperature according to thermody-
namic equilibrium, appropriate catalysts had to
be developed. In these processes, a so-called rich
gas having a methane content of ca. 65 vol % is
produced from naphtha and steam by a slightly
exothermic reaction in a shaft reactor at 400
– 490 ◦ C. Because the calorific value and spe-
cific gravity of this gas are too high, compared
with pertinent standards for town gas, part of
it must be reformed in a downstream tubular
reformer using commercial catalysts and then
remixed with the residual methane-rich gas. An-
other method of obtaining a leaner gas is to add
nitrogen or air. Many European cities built plants
of this type with town gas capacities up to 1 ×
106 m3 (STP)/d.
Plants that converted propane – butane to
town gas via externally heated tubular reformers
were built particularly for small capacities. Part
of the propane – butane was added to increase
the calorific value of the reformed gas after car-
bon monoxide shift conversion. A few plants
produced town gas by reforming natural gas in
externally heated tubular reformers for transi-
tional periods. This was done mainly when the
consumers’ existing piping systems and burners
were to be used, even if a loss in efficiency had
to be accepted in converting natural gas to town
gas.
Oil gasification by partial oxidation (Shell,
Texaco, Lurgi; see Section 3.2.2) has not be-
come important in town gas production because
of the high investment cost of such plants. The
gases produced, consisting essentially of hydro-
gen and carbon monoxide must be carbureted to
comply with standards.
Along with the development of gas produc-
tion processes, downstream gas conditioning
and gas cleaning units were adapted as well.
Carbon monoxide shift conversion plants often
reduced the carbon monoxide content to < 3
vol %, sometimes even to < 1 vol %, to elimi-
nate the danger of poisoning.
The composition of town and grid gas is given
in Tables 42 and 43 (Chap. 8). Group A in these
tables corresponds to town gas; Group B, to grid

gas; and the first gas family, to town and grid
gases combined.
1.1.4. Biogas and Landfill Gas (→ Methane)
Biogas is the gaseous reaction product from
anaerobic digestion of wastewater having a high
BOD value or of sludge from wastewater treat-
ment plants. It is used solely as fuel for combus-
tion engines to meet the power requirements of
the treatment plant.
Landfill gas is produced by the degradation
of organic matter in the waste disposed of in
landfills under anaerobic conditions. Because
access to oxygen is not strictly controllable,
aerobic degradation may occur simultaneously,
producing water and carbon dioxide. Landfill
gas is recovered via pipelines buried in the land-
fill. For existing landfills, wells are drilled and
lined with tubes to allow the gases to be ex-
tracted. Landfill gas is used mostly as fuel gas
for cogeneration and in combustion engines af-
ter suitable purification.
Composition. Biogas is composed of 60 –
70 vol % methane and 30 – 40 vol % carbon
dioxide, depending on the feed and digester tem-
perature (mesophilic – thermophilic).
Landfill gas is composed of 50 – 55 vol %
methane, 41 – 45 vol % carbon dioxide, and 1
– 4 vol % nitrogen.
Depending on the nature of landfill waste, the
gas may also contain considerable amounts of
halocarbons.
1.1.5. Rich Gas and Substitute Natural Gas
(SNG)
Basis of Production. As a result of the
doubts concerning gas supplies and their avail-
ability to the industrial nations in the 1970s ef-
forts were made to produce synthetic natural gas
from the plentiful coal supplies. These efforts
were feasible where natural gas accounted for
a high percentage of primary energy and cheap
domestic coal was available. Thus, a plant was
built in North Dakota (United States) which has
gone into operation in 1984, producing ca. 3.9
× 106 m3 (STP)/d of SNG from lignite. In this
Gas Production 9
plant, lignite is gasified in Lurgi pressure gasi-
fiers, and the methane content required is ad-
justed by reacting carbon monoxide and hydro-
gen from the raw gas in a methanation stage
downstream of the gas cleaning unit. In addi-
tion, the Lurgi gasification process has been de-
veloped further to produce SNG more economi-
cally by increasing gasification pressure to 10.0
MPa (Ruhr 100, see Section 4.4). Here, more
than 50 vol % of methane recoverable from coal
is produced in the gasification stage proper.
Heavy vacuum residues can also be used
as feedstock for SNG production. However, as
in coal-based plants, capital investment is rela-
tively high. The discovery of huge new natural
gas resources in some areas of the world during
the past few years has made the production of
SNG less attractive.
Composition. Rich gases have a higher
calorific value than grid gas, with gross calorific
values from about 25 000 kJ/m3 (STP) upward.
A rich gas produced from naphtha (British Gas
or BASF – Lurgi process) has the following typ-
ical analysis, in percent by volume:
Carbon dioxide 21.6 Hydrogen 12.5
Carbon monoxide 0.3 Methane 65.6
Substitute natural gas should differ as little
as possible from natural gas. It must be condi-
tioned so that it can be substituted for natural
gas. This depends on the following parameters:
higher heating value, density, and Wobbe index
(see Section 8.2.1.3).
In addition the specified content of impuri-
ties, particularly sulfur, must not be exceeded.
Typical SNG produced in a coal gasification
plant in North Dakota has the following analy-
sis, in percent by volume (unless otherwise stip-
ulated):
Methane 96.3 Nitrogen + argon 1.1
Carbon monoxide 0.02 Carbon dioxide 1.2
Hydrogen 1.38 Hydrogen sulfide 4 ppm
1.2. Raw Materials for Gasification
Gaseous Fuels. Natural gas as raw material
is of paramount importance for gasification or
reforming (the term reforming is used more
10 Gas Production
commonly for gases) in externally heated tubu-
lar reformers to yield synthesis gas for various
applications. Plants also reform natural gas by
partial oxidation. The composition of natural
gases is not important for the technology to be
applied, as long as their inerts content is negligi-
ble. However, if the nitrogen content rises above
5 – 10 vol %, this may have consequences for
the design of ammonia synthesis gas plants op-
erated on the tubular reformer principle.
In certain new energy scenarios, natural gas
still plays an important role. Thus, the energy
required for natural gas reforming may be sup-
plied — at least partially — by solar collectors or
high-temperature nuclear reactors. Liquid motor
fuels can be synthesized from synthesis gas. In
this way, thermal energy, which is difficult to
store and utilize, is converted to energy carriers
better adapted to the requirements.
Coke oven gas (→ Coal Pyrolysis) is of mi-
nor importance for producing synthesis gas be-
cause special expenditures are necessary to re-
move various impurities from the coke oven gas,
and compression costs are high. In older plants,
coke oven gas was separated into its individual
components by fractionated condensation and
distillation at low temperature rather than being
reformed (the content of methane and higher hy-
drocarbons is low anyway); these components
were then used for synthesis gas production.
Liquid Fuels. In most cases, various frac-
tions of crude oil are used for gasification. Only
in very rare cases is unrefined crude oil used
directly for gasification because neither its eco-
nomic nor its technical considerations are opti-
mum.
Liquefied petroleum gas (LPG, a propane –
butane mixture; → Liquefied Petroleum Gas) is
used for the production of town gas, particularly
in smaller capacity plants, and for peak shaving.
It is virtually sulfur-free and can be processed
without significant problems. Light naphtha is
utilized for larger town gas plants and for the
production of synthesis gas. Generally, fractions
boiling at 40 – 110 ◦ C are used, but full-range
straight-run naphtha with a boiling end point of
150 – 200 ◦ C may also be employed. Depend-
ing on its origin, this naphtha has a sulfur con-
tent between 30 and 300 ppm. Naphtha must be
completely desulfurized because almost all con-
ventional processes for the production of town or
synthesis gas include a reaction stage involving
catalysts that are very sensitive to sulfur poison-
ing.
In some cases, LPG and naphtha have also
been converted to town and synthesis gas by par-
tial oxidation (thermally or catalytically) with
oxygen or oxygen-enriched air. For catalytic par-
tial oxidation, desulfurization to 20 – 50 ppm is
sufficient.
Synthesis gas is produced from high-boiling
residues by partial oxidation with oxygen. Orig-
inally, the high-boiling fraction (initial boiling
point above 350 ◦ C) from atmospheric distilla-
tion units of refineries (→ Oil Refining) — the
heavy fuel oil — was used for this purpose. To
date even higher viscosity fractions from vac-
uum distillation and conversion plants are being
used increasingly. Because of the more stringent
requirements imposed by environmental legisla-
tion, these heavy oils can no longer be burned in
boiler houses and are, therefore, cheap raw mate-
rials for gasification, which also eliminates var-
ious pollutants in the residue such as sulfur and
heavy metals. To be used in gasification plants,
the heavy oil must be suitable for pumping and
spraying. Therefore, the oils are preheated to at-
tain the required viscosity.
The ash content of the heavy oils and the com-
position of the ash affect the operating temper-
ature of gasification plants and the service life
of the refractory lining. Vanadium and nickel in
ash are particularly harmful.
Apart from petroleum fractions, other liquid
fuels may be used for gasification, although they
are not very important. These include:
1) tars from bituminous coal and lignite for gasi-
fication by partial oxidation;
2) fractions from shale oil (→ Oil Shale) produc-
tion, particularly heavy fractions, for gasifica-
tion by partial oxidation;
3) methanol for producing peak shaving gas in
catalytic town gas plants;
4) hydrocarbon condensates from natural gas
production for gasification by partial oxida-
tion; and
5) waste from chemical plants (e.g., isobutyr-
aldehyde).
Purity Requirements for Liquid and
Gaseous Fuels. Raw materials for gasification
plants using catalysts must generally be very

pure. Therefore, in most cases, such plants
are equipped with special upstream purification
units. A certain tolerance regarding the con-
tent of impurities can be accepted in cyclic pro-
cesses that regenerate catalysts in the respective
cycles. However, continuous processes impor-
tant to modern technology require exceptionally
pure fuels, especially with respect to sulfur com-
pounds. Catalysts used for these processes thus
permit the use only of gaseous fuels (natural gas)
and of liquid hydrocarbons up to a boiling end
point of ca. 200 ◦ C.
Generally, the lower the operating temper-
ature of the catalytic process, the lower is the
residual sulfur content that can be tolerated in
the raw materials. How adverse an effect sulfur
compounds in the gas have on the active sites of
catalysts can be derived from equilibrium con-
ditions governing the reaction of the metallic
phase of the catalyst with the sulfur compounds.
Most gasification catalysts contain nickel as an
active substance. At constant partial pressure of
sulfur compounds in the gas, nickel sulfide for-
mation increases with decreasing temperature; a
sulfided catalyst no longer provides the desired
results regarding reaction direction (danger of
carbon formation), speed, and selectivity.
Therefore, light hydrocarbons are desulfur-
ized to < 0.1 ppm of sulfur upstream of plants
operated at low catalyst temperature (400 –
700 ◦ C). The sulfur content may often be higher
by one or two orders of magnitude in catalytic
processes operating above 850 ◦ C.
Solid Fuels. Various solid fuels are not all
equally suitable for gasification. In addition, dif-
ferent gasification processes have different fuel
requirements.
Because endothermic gasification reactions
should be as complete as possible, the suitability
of solid fuels for gasification improves as their
reactivity increases. This reactivity can be corre-
lated with the oxygen content, which decreases
with increasing carbonization (i.e., with increas-
ing age of the fuel).
The classification and designation of various
types of coal are different in individual industrial
countries (→ Coal, Chap. 4). As a rule, however,
they depend on volatile matter, which almost al-
ways means classification by age of the coal.
Gas Production 11
Additionally, the following properties of fu-
els are essential for assessing their suitability for
gasification:
Ash content Coal grain size
Water content Melting behavior of the ash
Sulfur content Behavior of the coals on heating
Caking properties
Because coal gasification adds considerably
to the costs of upgraded energy (i.e., the gas),
coal used for this purpose should be as cheap
as possible. Wherever possible, only coal that is
not suitable for other applications and, therefore,
has a low market price should be used. Coal pro-
duced by open-pit mining is of special interest
for gasification.
Almost all solid fuel such as wood, peat, lig-
nite, young and old bituminous coal, and coke,
including petrol coke, has been used for gasifi-
cation. In the future, more use should be made
of lignites and younger noncaking or caking bi-
tuminous coal, as well as coal with a high ash
content (20 – 50 wt %) or sulfur-rich coal which
is rarely suitable for other applications.
With regard to various types of petrol coke
(delayed, fluid, Lurgi – Ruhr gas (LR) coke, →
Oil Shale, ), their high sulfur and heavy-metal
content (→ Petroleum Coke) renders combus-
tion increasingly difficult in view of pollution
control measures. Petrol coke is, therefore, turn-
ing into a new potential raw material for gasifi-
cation.
Gasification of wood has been revived be-
cause of increasing interest in renewable raw
materials. Emphasis is mainly on the production
of clean fuel gas (low sulfur content of wood),
but synthesis gas production is also possible with
modern fluidized-bed processes.
Suitability of Fuels for Gasification. Con-
siderable differences exist in the complexity of
gasification technology applied, depending on
whether solid, liquid, or gaseous fuels are used.
A general rule is that capital cost and consump-
tion figures are higher for solid than for liquid
fuels, and for liquid higher than for gaseous fu-
els. Therefore, in the production of particular
gases, mere comparison of specific energy prices
of various fuels is insufficient; individual costs
for gasification must be considered as well (see
Table 2).
12 Gas Production
Table 2. Comparison of capital cost and energy requirements for
an ammonia plant and a methanol plant with a capacity of 1000 t/d
based on gaseous, liquid, and solid fuel
Natural Heavy
gas oil
Ammonia plant
Capital cost, % 100 170
Energy requirements, % 100 115
Methanol plant
Capital cost, % 90 150
Energy requirements, % 95 105
To make end products competitive, the spe-
cific energy price of coal must be lower than
that of heavy oil, and the latter must be lower
than that of natural gas. In principle, this also
applies to other solid and liquid fuels with re-
gard to the complexity of the conversion plant
based on these particular feedstocks.
Even if fuels of the same physical state are
compared, great differences exist in the proper-
ties of individual substances, which also affect
their suitability for gasification.
1.3. Physicochemical Basis for Gas
Production
Gasification can be described by overall chem-
ical reactions, from which conclusions may be
drawn regarding the conversion of materials and
heat of reaction.
Gasification of solid and liquid fuels involves
heterogeneous reactions at the phase boundary
of particles or droplets and homogeneous reac-
tions in the gas phase. The latter include reac-
tions of components that devolatilize at operat-
ing temperature.
The following principles form the basis for
calculating gasification processes:
1) Material Balance. In establishing a material
balance, the total number of atoms of the in-
dividual elements in the reactants is equalized
to that in the products, irrespective of the dis-
tribution of the elements between the individ-
ual components (principle of conservation of
mass).
2) Energy Balance. Energy balance is based on
the principle of conservation of energy. Con-
sequently, energy supplied to the system (en-
thalpy of reactants and heat supplied) is equal
to energy removed from it (enthalpy of prod-
ucts and heat removed). In determining en-
thalpy, formation and phase change energies
must be considered.
Coal 3) Chemical Equilibrium. The equilibrium com-
position of the gasification product is deter-
mined by the temperature-dependent equilib-
225
135
rium constants of reactions going on in the
system and by the operating pressure.
200 4) Chemical Kinetics. Because equilibrium is
125
not attained when residence time is too short
(for example, because the temperature is too
low), the composition of the gasification prod-
uct in this case is determined by the kinetics of
the reactions. In addition, transport phenom-
ena, such as boundary layer or pore diffusion,
may have some influence (see page 15.
Practical calculation leads to nonlinear equa-
tion systems in which the number of unknown
quantities is determined essentially by the num-
ber of components in the raw gas. The solu-
tion may be found iteratively or — if appropri-
ate routines are used — simultaneously. Calcu-
lations are particularly complicated when chem-
ical kinetics must be considered.
Reaction Enthalpy of Gasification. Gasifi-
cation reactions can be described by many differ-
ent equations. To calculate the reaction enthalpy
of gasification, however, a limitation to certain
characteristic reaction groups is sufficient. The
reaction enthalpy of all other reactions can be
derived by combining these basic equations, and
individual reactions have no influence on the to-
tal heat balance of a sequence of reactions if the
same feedstocks are turned into the same prod-
ucts (Hess’s law).
The reaction groups characteristic of gasifi-
cation can be subdivided as follows (∆H refers
to 0 ◦ C and 0.1 MPa as reference state; ∆H is
negative for exothermic reactions and positive
for endothermic reactions):
1) Reactions with molecular oxygen (combus-
tion)
C+1/2 O2
CO ∆H = −110.62 kJ/mol (1)
CO+1/2 O2
CO2 ∆H = −283.15 kJ/mol (2)
H2 +1/2 O2
H2 O ∆H = −242.00 kJ/mol (3)
Cn Hm + (n+m/4) O2
n CO2 +m/2 H2 O (4)
 Gas Production 13

For example,
CH4 +2 O2
CO2 +2 H2 O ∆H Cn Hm +2 n H2 O
n CO2 + (m/2+2 n) H2 (9)
= −802.86 kJ/mol (4a)
can be determined by
C2 H6 +7/2 O2
2 CO2 +3 H2 O∆H
∆H (Eq. 9) = ∆H (Eq. 8) +n ∆H (Eq. 7)
= −1428.8 kJ/mol (4b)
because Equation (9) may be considered a
C3 H8 +5 O2
3 CO2 +4 H2 O∆H combination of Equations (8) and (7).
= −2045.4 kJ/mol (4c) 3) Reactions with carbon dioxide
C+CO2
2 CO ∆H = +172.54 kJ/mol (10)
The reaction enthalpy of combustion of other
gaseous or liquid fuels is described in the lit- (Boudouard reaction)
erature (e.g., [2 – 4]).
For partial combustion of gaseous or liquid Cn Hm +n CO2
2 n CO+m/2 H2 (11)
fuels to carbon monoxide and steam,
Cn Hm + (n/2+m/4) O2
n CO+m/2 H2 O (5) For example,
CH4 +CO2
2 CO+2 H2 ∆H
the reaction enthalpy can be calculated from = +247.44 kJ/mol (11a)
the enthalpies of Equations (4) and (2) as fol-
lows: C2 H6 +2 CO2
4 CO+3 H2 ∆H

∆H (Eq. 5) = ∆H (Eq. 4) −n ∆H (Eq. 2) = +429.82 kJ/mol (11b)

2) Reactions with steam C3 H8 +3 CO2
6 CO+4 H2 ∆H

C+H2 O
CO+H2 ∆H = +131.38 kJ/mol (6) = +621.53 kJ/mol (11c)

CO+H2 O
CO2 +H2 ∆H = −41.16 kJ/mol (7) Generally, the reaction enthalpies for hydro-
carbon gasification with carbon dioxide (Eq.
(homogeneous water gas reaction, shift con- 11) are obtained from the enthalpies of Equa-
version) tions (8) and (7) as follows:
∆H (Eq. 11) = ∆H (Eq. 8) −n ∆H (Eq. 7)
Cn Hm +n H2 O
n CO+ (m/2+n) H2 (8)
4) Hydrocarbon decomposition reactions (soot
formation)
For example,
Hydrocarbon decomposition is described by
CH4 +H2 O
CO+3 H2 ∆H
Cn Hm
n C+m/2 H2 (12)
= +206.28 kJ/mol (8a)

C2 H6 +2 H2 O
2 CO+5 H2 ∆H For example,

= +347.50 kJ/mol (8b) CH4
C+2 H2 ∆H
= +74.91 kJ/mol (12a)
C3 H8 +3 H2 O
3 CO+7 H2 ∆H
= +498.06 kJ/mol (8c) C2 H6
2 C+3 H2 ∆H
= +84.74 kJ/mol (12b)
The enthalpy of the reaction of fuels with
steam to produce carbon dioxide and hydro- C3 H8
3 C+4 H2 ∆H
gen = +103.92 kJ/mol (12c)
14 Gas Production

may be considered the reverse of hydrocarbon

formation from its elements and is essential
for the gasification of hydrocarbons.
The reaction enthalpy can be calculated from
the combustion enthalpies of the reactants:
∆H (Eq. 12) = ∆H (Eq. 4) −n ∆H (Eq. 1)
−n∆H (Eq. 2) −m/2 ∆H (Eq. 3)

In calculating the main gas components, side

reactions of sulfur compounds (H2 S, COS, etc.)
and nitrogen compounds (NH3 , HCN) are gener-
ally neglected because they have no great effect
on the numerical distribution of the main gas
components. If detailed information on the dis-
tribution of secondary components is required,
further calculations can be made and the results
used for the main gas components.
Chemical Equilibrium. The gasification re-
actions represented by Equations (1) – (12) are
never complete in either of the two possible di-
rections but tend to reach an equilibrium ex-
pressed by the equilibrium constant K p . For
Equation (8 a), for example, this constant is
given by
pCO ·p3H2 xCO ·x3H2
Kp = = P 2 = f (T )
pCH4 ·pH2 O xCH4 ·xH2 O
where x i represents the mole fraction and pi the
partial pressure of each of the four components,
P the total pressure, and T the temperature.
For Equation (7), the carbon monoxide shift
conversion (which in nearly any case has to be
considered) the equilibrium constant is given by
pCO2 ·pH2 xCO2 ·xH2
Kp = = = f (T )
pCO ·pH2 O xCO ·xH2 O
In comparison to the steam reforming reaction
(8 a) the equilibrium composition of the shift
conversion is not influenced by the total pres-
sure, because simply spoken, the number of
molecules on the right and on the left side of
Equation (7) is identical. The temperature de-
pendence of the equilibrium constant (log K p
vs. 1/T ) is shown in Figure 1.
According to the laws of thermodynamics,
the equilibrium constant K p of a reaction can be
calculated by means of the Gibbs free energy of
the reaction or the free formation energies of the
reactants.
Figure 1. Water gas equilibrium, K p = f (1000/T )
Strictly speaking, the equilibrium constant
K p in the above form applies only to ideal gases.
At increased pressure (total of ca. 1.0 MPa or
more) and near the boiling points of the liquids,
the appropriate partial fugacities should be used
instead of partial pressures. These fugacities al-
low for the real behavior of individual gas com-
ponents. However, in practice, partial pressures
can be used for the calculation with sufficient
accuracy in most cases.
In heterogeneous reactions, partial pressures
of the solids are not taken into account because
they are regarded as a function of temperature
alone, which is included in the equilibrium con-
stant K p . However, the free formation energy
of the solids must be considered in a thermody-
namic calculation of the equilibrium constants.
The three reactions described by Equations
(7), (8 a) and (10) are almost always sufficient
to calculate the theoretical product gas compo-
sition of various gasification processes. Table 3
shows the equilibrium constants of these three
reactions at different temperatures. In addition
equilibrium constants for heterogeneous meth-
ane decomposition (Eq. 12 a) are given as an
example of hydrocarbon decomposition. This
equilibrium may also be derived from Equations
(7), (8 a), and (10). Additionally equilibrium
constants for COS hydrogenation and hydrolysis
are included (see Section 5.2).
COS+H2
H2 S+COCOS+H2 O
H2 S+CO2
The temperature dependence of the equilib-
rium constants can be calculated with an equa-
tion of the following type
 Gas Production 15
Table 3. Temperature-dependent equilibrium constants of various reactions
Equation (7) (8 a) (10) (12 a) COS COS hydrolysis
hydrogenation
Unit for K p bar2 bar bar
Temperature, ◦ C
100 12.4 4.39×104
200 19.1 4.26×103
300 38.5 6.13×10−8 3.60×10−7 4.36×10−3 24.4 940
400 11.5 5.54×10−5 8.55×10−5 5.56×10−2 28.0 323
500 4.82 9.16×10−3 4.99×10−3 3.76×10−1 30.3 146
600 2.51 4.88×10−1 1.16×10−1 1.66 31.5 79.1
700 1.52 11.8 1.42 5.41 32.1 48.7
800 1.02 159 11.0 14.1 32.2 32.9
900 7.41×10−1 1.38×103 59.8 31.2 32.0 23.7
1000 5.71×10−1 8.63×103 249 60.6
1100 4.60×10−1 4.12×104 845
1200 3.84×10−1 1.59×105 2.43×103
1300 3.30×10−1 5.16×105 6.08×103
1400 2.91×10−1 1.48×106 1.36×104
1500 2.61×10−1 3.69×106 2.79×104

log Kp = A+B/T +C logT +D·T +E·T 2 A general assessment of tendencies in gasifi-

cation reactions is facilitated by the Le Châtelier
where T is the absolute temperature in Kelvin. – Braun principle that a system in equilibrium
For the various equilibria used in this article the tries to evade a change forced upon it. For ex-
values of the constants A – E are given in Table ample, in Equation (8 a), an increase in total
4. (The data of Tables 3 and 4 were taken from pressure results in increased methane formation
the ASPEN program [5] which uses in this case because the number of gaseous molecules on
the correlations cited in [6]. Minor differences the right side of Equation (8 a) is higher than
with respect to other literature data may occur.) that on the left. A pressure increase in reactions
proceeding without a change in the number of
Table 4a. Values of coefficients for calculating the equilibrium molecules, such as the homogeneous water gas
constants of various reactions as a function of absolute temperature reaction (Eq. 7) has almost no effect.
Equation (7) (8a)
A −8.000980 −18.98177
B 2456.620 −9520.569
Reaction Sequence for Various Gasifica-
C 1.984098 10.91012 tion Processes. No statements can be made
D −0.3329441×10−3 −0.319556×10−2 on the basis of thermodynamics regarding the
E 0.563315×10−7 0.3631894×10−6 chronological sequence of gasification reac-
tions. Calculations must include reaction ki-
Table 4b. Values of coefficients for calculating the equilibrium netics. Frequently, however, the required data
constants of various reactions as a function of absolute temperature
are not available. Approximation methods must
Equation (10) (12a) then be used to calculate product gas compo-
A 2.220419 −21.61666
B −8709.775 −2875.50 sition. A common method involves use of K p
C 2.495100 9.505546 values which, according to experience, reflect
D −0.6399432×10−3 −0.3694027×10−2 the actual final state but pertain to a tempera-
E 0.5280003×10−7 0.5233708×10−6 ture other than that prevailing at the end of the
reactor.
Table 4c. Values of coefficients for calculating the equilibrium Some processes employ catalysts to acceler-
constants of various reactions as a function of absolute temperature
ate the reaction and enhance reaction kinetics in
Equation COS hydrogenation COS hydrolysis
order to approach equilibrium. Selective cata-
A 5.956145 4.485945
B −566.2154 1568.825 lysts promote desirable reactions at the expense
C −1.309130 −1.681947 of undesirable ones (e.g., carbon formation ac-
D 0.5766548×10−4 0.7452208×10−3 cording to Boudouard). Generally, reaction rate
E −0.1222679×10−7 −0.1160356×10−6
increases as temperature increases. Gasification,
16 Gas Production
therefore, approaches equilibrium more easily at
higher than at lower temperature.
Tubular Reactor Reforming. When reform-
ing hydrocarbons, especially methane, in exter-
nally heated tubular reactors, conversion of the
hydrocarbons with steam to yield carbon oxides
and hydrogen (according to Eqs. 8 and 9) must
be considered basic reactions. The composition
of the product gas is determined by the simul-
taneous equilibrium between Equations (7) and
(8 a).
Because soot formation should be sup-
pressed, the Boudouard reaction (Eq. 10) and
hydrocarbon decomposition (Eq. 12 and, espe-
cially, 12 a) are essential for an assessment of
the reaction system.
Rich-Gas Process. When naphtha is re-
formed catalytically with steam in a shaft reac-
tor to yield gases with a high methane content,
the endothermic gasification reactions (Eqs. 8
and 9) must be considered as starting reac-
tions, whose products are then transformed in
an exothermic methanation reaction described
by Equation (8 ). The final condition of the re-
forming process is determined by Equations (7)
and (8 a).
Oil Gasification. In oil gasification with oxy-
gen and steam, partial combustion of hydrocar-
bons (Eq. 4), as well as steam and carbon diox-
ide gasification of carbon (Eqs. 8 and 11), must
be considered to proceed more or less simulta-
neously. Product gas composition is determined
by the final state of the simultaneous equilibrium
among the reactions described in Equations (7),
(8 a), and (10).
Coal Gasification. The first step in a coal
gasification reaction (e.g., with oxygen and
steam in countercurrent mode of operation) is
exothermic combustion of carbon to carbon
dioxide, according to Equations (1) and (2). The
carbon dioxide formed then reacts with hot car-
bon to yield carbon monoxide in an endothermic
reaction (Eq. 6). This in turn reacts with steam to
produce either hydrogen and carbon dioxide (ac-
cording to Eq. 7) or methane and carbon dioxide
(by the reverse of Eq. 11 a). The latter occurs
particularly at increased gasification pressure.
Carbon monoxide and hydrogen are also pro-
duced by direct endothermic carbon gasification
with steam (Eq. 6). In entrained-flow gasifica-
tion processes, the reaction sequence described
is mostly overlapping. The mode of reaction es-
sentially determines the temperature profile in a
gas producer.
The composition of gasification gas is deter-
mined by a more or less accurate adjustment of
the simultaneous equilibrium among the shift
conversion reaction (Eq. 7), the methane reform-
ing reaction (Eq. 8 a), and the Boudouard reac-
tion (Eq. 10).
1.4. Characteristics of the Basic
Processes
In most cases, the aim is to produce gases with
high hydrogen and carbon monoxide content.
This applies to all synthesis gases and also to
town gas. Depending on the particular require-
ments, the carbon monoxide content may be re-
duced with steam to yield hydrogen and carbon
dioxide. To produce such gases from various
solid, liquid, and gaseous fuels, heat must be
supplied to support the endothermic reactions.
Thus, different processes can be classified ac-
cording to the type of heat supply.
On the other hand, processes for producing
gases with high methane content, such as rich
gas and SNG, in principle require no exter-
nal heat supply because methane formation is
exothermic. Therefore, the process characteris-
tics of this group are different.
Trends in the past decades have shifted from
processes operated under atmospheric condi-
tions to those operated at elevated pressure. This
has resulted in economic advantages because
the subsequent chemical syntheses [ammonia,
methanol, oxo (→ Oxo Synthesis ) and Fischer
–Tropsch synthesis (→ Coal Liquefaction)] op-
erate at more or less elevated pressure, which re-
moves the cost of compressing the high-volume
synthesis gas. Moreover, plants operating under
pressure can be designed for higher capacity due
to their smaller gas volume, which again means
savings in capital costs.
An essential criterion is whether catalysts
are used. With catalysts, a better approximation
to reaction equilibria is attained and undesired
byproducts are mostly avoided. However, cata-
lysts can thus far be used successfully only for
gaseous feeds and for distillate liquid feeds.
Cyclic Processes. Cyclic processes use heat
carriers consisting of refractory brick lining (in

regenerators, air heaters, etc.) or beds of ceramic
material, which may be appropriately impreg-
nated to impart catalytic properties to them. Re-
generative heating is provided by hot flue gases
from the combustion of liquid or gaseous fuels.
During gasification, the heat carrier transfers its
heat to the raw material to be converted. The
process is suitable for liquid and gaseous feed-
stocks. Any carbon black deposited during the
reforming period can be burned off after the sys-
tem is switched back to heating. The process is
not suitable for operation at elevated pressure.
Processes using circulating heat carriers
are similar to cyclic gasification except for being
continuous processes circulating the heat carrier
in a closed loop. This carrier is heated by hot flue
gases and then fed to a reaction section in which
its heat is used for gasification. In addition to sen-
sible heat, some heat carriers used in the past also
produced heat through reaction with gas compo-
nents (producing CaCO3 from burned lime and
CO2 ). Any carbon formed in the process can be
burned off in the heating zone. The process is
generally suitable for gaseous, liquid, and solid
fuels. The circulating heat carrier may consist
of granular catalytic or noncatalytic solids, or of
liquids (such as slag baths) and circulating gas.
Although system design does not altogether ex-
clude elevated operating pressure, the necessary
design and operating conditions would be diffi-
cult to meet.
Autothermal Processes. Autothermal pro-
cesses produce the heat required for gasifica-
tion through partial combustion of the fuel to
be converted in the reactor. Oxygen or air — if
nitrogen in the air is not a ballast in the prod-
uct gas — is added for this purpose. The process
may operate with or without catalysts. If cata-
lysts are used, the temperature can be kept lower
because a closer approach to equilibrium is en-
sured. However, the catalytic process cannot be
used to gasify heavy and residual oils because
most of these oils contain ash particles that con-
taminate the catalyst. Also, because of the ash
content, catalysts for coal gasification are not ap-
plied, so far. Either the catalyst would have to be
very cheap so that it could be disposed of along
with the ash, or it would have to be recovered by
a very complex procedure.
Gas Production 17
Processes applying baths of molten slag, iron,
or salts as heat carriers and reaction promoters
have been used and are still being developed.
A characteristic of autothermal processes is that
the oxygen added to generate heat is chemically
bound in the product gas, so the ratio of hydro-
gen to carbon monoxide in the product is lower
than in other processes. This type of process is
applied to solid, liquid, and gaseous fuels.
Processes Involving Externally Heated
Walls. Processes using externally heated walls
include tubular reforming, which is used widely
today. To keep the tube stresses resulting from el-
evated pressure and temperature to a minimum,
all tubular reformers employ a catalyst filling in
the tubes, which allows lower reaction tempera-
ture.
Modern materials permit tubes to be designed
for wall temperatures of ca. 900 ◦ C (in special
cases even 1000 ◦ C at atmospheric pressure) and
pressures up to 4.0 MPa. All gaseous hydrocar-
bons (with low unsaturated hydrocarbon con-
tent) and distillate liquid fuels are suitable feed-
stocks. When liquid hydrocarbons are used, de-
mands on the catalysts are extremely high. Vir-
tually ash-free fuels are used almost exclusively
to heat the tubes because ash constituents (salts,
metals) would damage tube walls.
Reactors with externally heated walls are also
used in gas production from solid feedstocks.
This process technology offers the opportunity
to employ nonfossil energy (heat from nuclear
reactors, solar energy) for gasification.
Rich-Gas Processes. Because no external
heat supply is required for rich-gas processes,
the equipment and process loops can be cho-
sen freely. In most systems, a catalyst is applied
because methane formation is favored by lower
temperature. Apart from the unfavorable equi-
librium position, the risk of carbon deposits re-
sulting from the Boudouard reaction is higher at
increased temperature, and other byproducts are
formed as well. All the processes operate at el-
evated pressure because this promotes methane
formation.
Because catalysts are highly sensitive with
respect to attrition, reactors are normally of the
fixed- rather than the fluidized- or entrained-bed
type. Raw materials must be virtually free of all
18 Gas Production
substances that may poison catalysts, particu-
larly sulfur compounds.
1.5. Product Gas Treatment
Each gasification plant requires gas treatment fa-
cilities to purify product gases and also, in many
cases, to condition them. Whereas the gas pu-
rification system eliminates the components that
would affect downstream processing or utiliza-
tion of these gases, the purpose of a condition-
ing system is to adjust gas components to the
appropriate ratio. The ratio of hydrogen to car-
bon monoxide, especially, must be matched to
the requirements of downstream synthesis or re-
duction units and other gas consumers.
The task of gas purification and conditioning
is most complex downstream of plants gasify-
ing solid fuels. Capital investment in these pu-
rification units can be much higher than that re-
quired for the gasification plant itself. Treatment
of gases produced through gasification of high
molecular mass liquid hydrocarbons (heavy oils,
vacuum residues) is also rather expensive. Gen-
erally, the smaller the molecules from which a
gas is produced, the lower is the capital invest-
ment required in treatment facilities. The costs
of gas purification are also strongly dependent
on the amount and type of impurities in the feed-
stock, particularly its content of sulfur and trace
elements.
Whereas most catalytic gasification pro-
cesses have some purification facilities (remov-
ing sulfur, lead, chlorine) upstream of the gasifi-
cation stage, the impurities in noncatalytic pro-
cesses should be removed only from the product
gas.
Impurities in the Gasification Gas. De-
pending on the type and composition of feed-
stock and the type of gasification process used,
a gas purification plant must handle the follow-
ing impurities:
– Dust (coal gasification)
– Carbonization products, tar, gas liquor (coal
gasification)
– Carbon (Heavy-oil gasification)
– Oxygen (coal gasification, oil gasification)
– Cyanic compounds (coal gasification, oil
gasification)
– Nitrogen oxides (coal gasification, oil gasifi-
cation)
– Carbon dioxide (all gasification processes)
– Hydrogen sulfide, carbonyl sulfide, organic
sulfur
– compounds (all noncatalytic gasification pro-
cesses)
– Ammonia (all gasification processes)
Other gas components, even if they occur
only in trace amounts, require specific measures
to prevent long-range damage or malfunction of
the plant. This is particularly true for the gasifi-
cation of coal and heavy oils. Such components
may include volatile metal compounds and high
molecular mass organic compounds.
1.5.1. Purification Processes
Because of the large number of impurities, along
with their widely varying content and combi-
nations, a variety of gas purification processes
are available to meet the requirements of down-
stream processing (synthesis, in particular) and
of industrial and municipal consumers (town
gas). Ammonia synthesis, for instance, tolerates
only ca. 5 ppm (mL/m3 ) of oxygen compounds
(e.g., O2 , CO, CO2 , and H2 O), and the sulfur
content must be < 1 ppm (mL/m3 ).
Methanol synthesis, on the other hand,
requires a sulfur content of < 0.1 ppm
(mL/ m3 ) and the stoichiometric ratio
(cH2 − cCO2 )/(cCO + cCO2 ) must be adjusted
to ca. 2 (see Section 7.1.2). To achieve this ra-
tio, the gas must contain a certain amount of
carbon monoxide — a factor that influences the
selection of gasification and purification pro-
cesses and also raises the question of whether
an additional process stage is required to con-
vert carbon monoxide into hydrogen and carbon
dioxide. Carbon dioxide need not be removed
completely so the general plant design can be
simplified considerably.
Reduction gases for direct reduction of iron
ore may contain sulfur on the order of 7 ppm
(mL/m3 ), but the content of water and carbon
dioxide should not exceed 5 vol %.
If several gas purification plants are com-
bined for optimum effect, perhaps including gas
conditioning facilities as well, possible interac-
tion should be checked carefully. Interactions
could occur because of solvents contained in the

gas, depending on their vapor pressure, different
operating behavior, etc. If fuel gas is produced
for a combined power cycle (see Section 7.3), the
gas purification plant must meet the load change
requirements of such plants.
Gas purification processes may be classified
as follows:
Adsorption. Adsorption describes the reten-
tion of impurities by solids, either through phys-
ical deposition or through chemical reaction
(chemisorption) (→ Adsorption , see also Sec-
tion 5.5). Whenever solids have to be reused
(e.g., for economic reasons), batchwise opera-
tion is necessary because the laden solids must
be regenerated.
Sulfur compounds are eliminated by using
beds of iron hydroxide and zinc oxide (espe-
cially for desulfurizing gaseous and liquid feed-
stocks for catalytic gasification). Activated car-
bon is favored in special cases for cleaning gases
containing high molecular mass organic sulfur
compounds.
Molecular sieves (→ Adsorption; → Zeo-
lites) have been developed for selective removal
of particular gases. They can be used not only for
carbon dioxide, sulfur compounds, and steam,
but also for diatomic gases.
Gas purification systems based on the ad-
sorption (and chemisorption) principle are pre-
ferred when small quantities of impurities must
be eliminated or small gas throughputs must be
purified.
Absorption. A general distinction is made
between physical and chemical absorption
processes. Physical processes (→ Absorption,
Chap. 1.4 , see also Section 5.4) are particu-
larly suitable for high pressure, high impurity
content, and large gas throughput. The processes
available differ in solvents used, mode of plant
operation, operating temperature, method of en-
ergy recovery, and potential for recovering sev-
eral components more or less separately. The
selection of appropriate solvents is determined
to a large extent by their specific solubility co-
efficients for the desired gases and by their se-
lectivity.
Chemical absorption systems (→ Absorp-
tion, Chap. 1.5) can be used at elevated or atmo-
spheric pressure. They are particularly suitable
whenever the absolute quantity of impurities to
Gas Production 19
be removed is small. Conventional processes
differ mainly in the degree of purity that can
be achieved and the amount of energy (normally
steam) required for regeneration. Numerous pro-
cesses also use some combination of physical
and chemical absorption principles.
Special Wash Processes. Special applica-
tions include the removal of solids entrained
with gases in the form of dust or carbon black,
dust-laden tar, and high molecular mass or un-
saturated hydrocarbons that tend to form gums.
1.5.2. Conditioning
For nearly all applications, gasification gases not
only must be purified but also conditioned to ob-
tain the optimum proportions of desirable gas
components (Sections 5.1, 5.2, 5.3).
Carbon Monoxide Shift Conversion.
Prominent among gas conditioning processes
is catalytic carbon monoxide shift conversion,
which is based on water gas equilibrium (Eq. 7).
By this process, the hydrogen content of a gas
can be increased as desired at the expense of its
carbon monoxide content. This is important not
only for ammonia synthesis but also for town
and grid gas production. The process permits
the gas to be adjusted to the standard density
and Wobbe index, and also enables nontoxic,
low-carbon monoxide town gas to be produced,
in conformity with current regulations.
Carbon monoxide shift conversion requires
the addition of steam, which can be done in
one of several ways. Steam at the appropriate
pressure may be added directly to the gas to
be converted. If steam is not available in suf-
ficient quantities and under economically jus-
tifiable conditions, a so-called saturator cooler
loop is often used. With this arrangement, gas
entering the conversion section is humidified by
circulating hot water, and unreacted steam in the
gas leaving this stage is recondensed and recy-
cled to the saturator. A distinction is also made
between high- and low-temperature conversion,
the latter being provided downstream of the for-
mer to reduce the residual carbon monoxide con-
tent of the gas to a minimum (e.g., for ammonia
synthesis). Shift conversion catalysts for sulfur-
free gases are based on iron (high temperature
20 Gas Production
shift) or copper (low temperature shift). They are
supplied as oxides and reduced during operation.
For gases containing sulfur compounds the shift
catalysts are based on cobalt and molybdenum.
They are active only as sulfides.
Methanation. Another gas conditioning
method is methanation, the conversion of car-
bon monoxide, carbon dioxide, and hydrogen to
methane according to Equations (8 a) and (9). A
methanation stage is included in many ammonia
synthesis plants to ensure a high degree of purity
of the synthesis gas. Similarly, a methanation
step is indispensable if a high-methane gas for
SNG production is to be obtained.
Other Processes. The following processes
may also be regarded as gas conditioning.
If the calorific value of town gas, grid gas, or
SNG is insufficient, the gasification gas may be
carbureted by adding C3 and C4 hydrocarbons
or, less frequently, small quantities of high mo-
lecular mass hydrocarbons. On the other hand,
too high a calorific value can be reduced by
adding nitrogen, air, or oxygen.
For certain syntheses, gases must be dried.
Drying is also necessary in pipelines, to protect
the piping from corrosion where a risk of water
condensation in the presence of carbon dioxide
exists. In addition, the formation of gas hydrates
is avoided.
Unlike town gas produced in the past from
coke oven batteries, the town gas obtained to-
day through gasification no longer contains any
chemical compounds that produce a manifest
odor. Therefore, such gases are now odorized
artificially so that leaks occurring in the piping
or at the consumer’s facilities can be detected
easily.
To recover particular components from a gas
stream (e.g., H2 from purge gas), pressure-swing
adsorption (PSA) (→ Adsorption) or membrane
processes (→ Membranes and Membrane Sepa-
ration Processes) can be used. The PSA principle
is based on the fact that the adsorption capac-
ity of molecular sieves (→ Zeolites) differs for
different gases. Generally, heavier or polar gas
components are adsorbed preferentially. When
a gas mixture is passed over a molecular sieve
bed, the component least amenable to adsorp-
tion (e.g., H2 ) remains in the gas whereas other
components are adsorbed.
Gas separation by membranes is based on
the differences in permeation coefficients of
different gas components. Permeation denotes
the sequence of absorption (solution) of the
component in the membrane material, diffusion
through the membrane, and desorption. The per-
meation rate of a species increases with its sol-
ubility and its diffusion coefficient in the mem-
brane material. Membranes may consist of ce-
ramic or metallic materials, organic liquids, or
polymers.
Both processes, PSA and membrane separa-
tion, can be used to advantage for gases at ele-
vated pressure.
To remove traces of higher hydrocarbons
(e.g., compressor lubricants) from gases, beds of
activated carbon are used. For recovery of low-
boiling compounds, as well as purification from
traces of higher boiling compounds, cryogenic
processes (→ Cryogenic Technology) can be ap-
plied. These employ primarily liquid methane or
nitrogen to absorb higher boiling gases such as
carbon monoxide.
1.5.3. Byproducts
Some gasification processes yield byproducts
along with the desired gas (see also Chap. 6).
A comparison of different gasification processes
should, therefore, always consider such byprod-
ucts and assess their importance. Environmental
protection, too, plays an important role because
it imposes stringent conditions on pollutant dis-
charge.
Many gasification plant feedstocks contain
sulfur, and sulfur often constitutes the main by-
product. Whether this is best recovered in the
form of elemental sulfur or sulfuric acid is worth
considering.
Other coal gasification processes have coke
as a byproduct.
Gasification involving coal carbonization
processes can produce a large number of byprod-
ucts such as tar, oil, gasoline, phenols, cresols,
ammonia, and organic acids. Certain liquid by-
products may even contain solids whose elimi-
nation would result in additional costs. Because
of this, processes have been developed to recycle
certain liquid fractions to the gasification plant
if their market value is low.

Heavy-oil gasification plants yield carbon as
a byproduct. Attempts to use it for special in-
dustrial applications have been successful, but
demand for the specific qualities of carbon is
limited. Therefore, processes are being devel-
oped to recycle most of this carbon to the gasifi-
cation stage. These and processes where carbon
is burnt in conventional power stations at little
extra cost are of major interest.
Gas liquor is a product of almost all gasifi-
cation processes. Depending on its composition
and on plant requirements, this gas liquor can
either be treated for use as boiler feed water or
cooling water, or be discharged to receiving wa-
ter via chemical or biological effluent treatment
plants.
2. Steam Reforming of Natural Gas
and Other Hydrocarbons
In the steam reforming process hydrocarbons are
catalytically converted by reaction with steam
into hydrogen and carbon oxides. This is the
most common method for producing hydrogen
or hydrogen: carbon oxide mixtures in the manu-
facture of important basic chemicals (e.g., am-
monia and methanol), oil refining, and in many
other industrial applications (e.g., iron ore re-
duction, hydrogenation of fats, production of
oxo alcohols).
Nowadyas natural gas predominates by far as
a feedstock over other hydrocarbons (e.g., naph-
tha, LPG, refinery gases) or coke oven gas which
are used only under special circumstances.
The catalytic steam reforming process in
tubular furnaces was invented in 1926 – 1928
by BASF [7]. This process was applied in the
United States for the first time in the early 1930s
at two commercial plants: (1) to produce hydro-
gen from natural gas for hydrogenation purposes
and (2) to synthesize ammonia. The process was
conducted under low pressure (0.4 – 1 MPa) and
at temperatures close to 800 ◦ C until the early
1950s; pressures up to 4 MPa and temperatures
up to 950 ◦ C are used today.
A special type of steam reforming which has
been in use even earlier than tubular steam re-
forming is autothermal reforming, also called
catalytic partial oxidation. This process differs
from catalytic steam reforming in that the re-
quired reaction heat is not supplied from outside
Gas Production 21
(furnace) but by internal partial combustion of
the feedstock with oxygen or air, admixed to the
process feed. As autothermal reforming is car-
ried out in refractory-lined vessels (cold shell),
higher pressures can be applied than in tubu-
lar steam reforming. Outlet temperatures up to
1000 ◦ C are usual. Due to the additional expen-
diture for oxygen supply and safe process con-
trol this technology was of minor general im-
portance in the past. Of common use, however,
is the process modification with air as oxidant
in ammonia synthesis. More recently, the oxy-
gen based gasification has been introduced into
methanol synthesis. “Combined reforming”, a
combination of tubular and autothermal reform-
ing, is recognized as the most efficient syngas
technology for large scale methanol plants at the
moment.
A comprehensive overview of recent devel-
opments in steam reforming technology is given
in [8].
Whereas in former years steam reformers
have been built nearly exclusively at locations
where there was requirement for hydrogen or
synthesis gas and products derived therefrom,
a big change has occurred since the 1970s, in
that particularly world-scale production plants
for ammonia and methanol have been built at
locations, where natural gas is available in abun-
dance (e.g., Trinidad, Borneo, Cape Horn).
Total hydrogen production by catalytic re-
forming currently (ca. 2000) amounts to over
400 × 109 m3 /a worldwide. Its uses can be bro-
ken down approximately as follows: 60 % for
ammonia production, 10 % for methanol pro-
duction, 25 % for petrochemical processes (hy-
drotreating, hydrodesulfurization, hydrocrack-
ing), and 5 % for other industrial purposes. The
cost of commercial production is about $ 0.10
per cubic meter of hydrogen. The catalytic steam
reforming process is especially low in emis-
sions. Only the off-gas from the steam reformer
contains, apart from carbon dioxide, a certain
amount of NOx and, depending on the feedstock,
sulfur dioxide.
2.1. Feedstocks
Natural Gas. Natural gases (→ Natural Gas
) are used as gasification feedstocks, either di-
rectly or after appropriate pretreatment. Table 5
22 Gas Production
gives examples of pretreated natural gases and
other hydrocarbon feedstocks. High-boiling hy-
drocarbons are largely eliminated before trans-
portation to prevent condensation in the distri-
bution system.
Particular attention must be paid to sulfur
compounds in natural gas. A gas suitable for cat-
alytic reforming has to be virtually free of these
compounds as sulfur is a strong poison to the
employed catalysts. High percentages of nitro-
gen are undesirable as well, except in ammonia
synthesis gas. For hydrogen – carbon monoxide
gases, nitrogen must be removed in a complex
operation. A certain percentage of carbon diox-
ide may be tolerated and even be beneficial in
methanol production.
The condensation fractions recovered from
casinghead gases (see Table 5) extend into the
naphtha range and contain higher hydrocarbons
that may create problems in catalytic reforming.
These fractions are handled similar to naphtha.
Reevaporated liquefied natural gas (LNG) is
free of all accompanying components such as
carbon dioxide, steam, sulfur compounds, and
C5+ hydrocarbons, which must be removed for
process reasons prior to liquefaction. It does not
contain any gas with a lower boiling point than
methane, such as nitrogen or noble gases (he-
lium). However, when obtained from the public
grid, LNG may contain sulfur compounds (used
as odorants; e.g., tetrahydrothiophene) and ni-
trogen (from calorific value – density condition-
ing).
Other Gases (see Table 6). Gases of differ-
ent qualities are derived from refineries, coking
plants, the chemical industry, steelworks, etc.
They are suitable not only as fuel gases but, in-
creasingly, as gasification feedstocks or as raw
materials for the chemical industry. As a typi-
cal example, hydrogen used in a refinery can be
produced by the conversion of refinery gases or
butane.
purge gases) from ammonia and methanol
synthesis or olefin production are also used for
gas production. Unsaturated hydrocarbons in the
residual gases are usually saturated by hydro-
genation before they are catalytically gasified
with steam. The top gas from some processes
for direct reduction of iron ore is upgraded by
adding fresh natural gas and used for gas produc-
tion. Coke oven gas, which was formerly used
mainly as town gas, is utilized today for ammo-
nia production or the reduction of iron ore.
Naphtha. At the beginning of the 1960s,
light naphtha was available in large quantities
for the production of town gas, ammonia, and
methanol. Since the 1973 oil crisis, it has been
used almost exclusively as a raw material for the
production of chemicals (especially ethylene).
Exceptions are town gas and synthesis gas pro-
duction in isolated areas where no natural gas is
available.
A distinction must be made between straight-
run virgin naphtha as obtained directly from
crude oil distillation and naphtha cuts from the
production facilities of a refinery, for example,
from a reforming unit (high-aromatic naphtha).
Naphthas differ according to geographical
origin of the crude. The main criteria for assess-
ing the suitability of a naphtha as a raw mate-
rial for gas production are its boiling range (low
boilers can be converted more easily); carbon:
hydrogen ratio; aromatic, olefin, and naphthene
contents; sulfur content; and content of metals or
other substances (e.g., lead, chlorine, which will
poison the catalyst). Table 7 shows the principal
characteristics of various naphthas.
Generally, low-boiling naphthas rich in alka-
nes are preferred for catalytic gasification be-
cause they are easier to convert and the cata-
lyst has a longer service life. In individual cases,
naphtha with a boiling end point up to 220 ◦ C,
mixtures of naphtha and kerosene, or kerosene
itself may be considered as raw materials.
Ammonia and Methanol. Ammonia and
methanol are occasionally used as feedstocks
for hydrogen production (in small units and for
peak shaving gas).
2.2. Natural Gas and Other Gaseous
Hydrocarbons
In the 1920s BASF developed a catalytic process
for endothermic conversion of gaseous hydro-
carbons with steam in externally heated tubes,
using nickel as a catalyst. Exchanges of experi-
ence with Standard Oil (New Jersey) and ICI in
the 1930s led — particularly in the United States
and England — to the first commercial applica-
tion of this process in the production of hydro-
 Gas Production 23
Table 5. Properties and composition of (treated) natural gases used as feedstocks for catalytic gas production

Table 6. Residual gases (Properties and composition of various residual gases and of a butane fraction
24 Gas Production
Table 7. Properties and composition of various naphtha feedstocks for gasification
Light naphtha Boiling range of full-range naphtha Heavy Treated naphtha a Condensate
naphtha Hydrotreated
Raffinate from
casing
head
gas
Density (15 ◦ C), 0.66 0.68 0.68
0.72 b
0.70 – 0.73 0.71 – 0.73 0.71 0.76 0.73 0.74
kg/L
Initial boiling point, 31 41 39 35 – 46 60 39 – 45 43 – 65 44 95 45 99 31
◦
C
b b
Intermediate boiling 70 69 96 – 105 98 127 91 134 110 138
point, ◦ C c
Final boiling point, 89 108 – 123150 – 165 66 180 – 185 165 – 187 200 190 197 206 344
◦
C 125
Molar mass 98 – 102
b
C/H mass ratio 5.17 5.24 5.375.70 – 5.77 5.4 5.8 5.54 6.0 6.0 5.61
b b b
Alkanes, vol % ca. 56.3 95 d b
81.3 48 72 b
71
75.5
b b
Olefins, vol % 0 0 0.10 – 0.2 0.1 0.3 – 0.6 1 1.5
b
Naphthenes, vol % ca. 2220 b 37.4 b
7.8 41 8 40 b
b
Aromatics, vol % 1.5 2.5 3.13.7 – 6.2 6.3 3.2 – 4.8 11 – 15 9.4 11 20 11
b b b b
Chlorides, mg/kg 1.2 3.0 – 1.21 – 3 4 16 – 30 0.1
4.0
Lead, mg/kg 0.02 0.02 0.90.01 0.1 0 b
< b b b

0.001
b
Sulfur, mg/kg 3.0 15 – 14 11 – 54 120 8 – 10 560 – 635 100 9 68
20
Higher heating 48 235 47 47 47 270 – 47 b 47 835 – 48 46 685 – 46 b
46 520 b b

value, kJ/kg 960 855400 275 895

Lower heating value, b 44 b 44 090 – 44 b 44 630 b b
43 335 b b

kJ/kg 465 170

a
From reformate.
b
Not measured.
c
Boiling point after 50 % reduction in volume.
d
Paraffins and naphthenes.

gen for hydrogenation and ammonia synthesis.
These plants operated at atmospheric pressure.
New reformer tube materials, especially the de-
velopment of centrifugally cast tubes, permitted
higher pressure in the gas production section,
which in turn improved plant efficiency consid-
erably.
2.2.1. Principles
Catalytic conversion of hydrocarbons with
steam to produce gases with high hydrogen and
carbon monoxide content, according to the re-
actions (8) and (8 a) — and always accompa-
nied by the shift conversion (Eq. 7) (see Sec-
tion 1.3) — is known as steam reforming. This
conversion is highly endothermic. It occurs in a
number of parallel, externally heated tubes (re-
former tubes) filled with a nickel catalyst.
After being preheated in heat exchangers or
fired heaters to ca. 500 ◦ C, the steam – hydro-
carbon mixture is heated further over nickel
catalyst in the tubes to the desired end tem-
perature of normally 800 – 900 ◦ C. Higher hy-
drocarbons (Eq. 8) are completely converted to
carbon monoxide and hydrogen, methane only
partially — corresponding to the reaction con-
ditions. The composition of the reformed gas
at the reformer outlet reflects the equilibria of
Equations (8 a) and (7). For specified condi-
tions (pressure, reformed gas temperature, steam
– hydrocarbon ratio), the composition of the re-
formed gas can, therefore, be calculated from
component balances and equilibrium conversion
rates. The steam: hydrocarbon ratio is an essen-
tial parameter in the steam reforming reaction
and must not be lowered arbitrarily, because low
ratios lead to carbon deposits on or in the cat-
alyst. Figure 2 shows the influence of pressure
and temperature on the composition of the re-
formed gas for a defined steam: methane ratio in
a methane reforming unit.

Figure 2. Equilibrium composition for methane reforming
at 500 – 1000 ◦ C and pressures (in the direction of the
arrows) of 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 MPa. Molar
steam: methane ratio 3.333 corresponding to 5 kg H2 O per
kilogram of carbon
Kinetics. The kinetics of catalytic steam re-
forming of methane are summarized in [9, 10]
and [11]. Many authors observe that the shift
conversion reaction described by Equation (7)
proceeds very fast so that the gas composition
may be assumed to be in equilibrium at every
point in the reformer tube — a proposition that
is not true for methane conversion which ap-
proaches to equilibrium only towards the outlet
of the tubes. Sulfur in the gas has no decisive in-
fluence on the shift conversion, but can decrease
the reaction rate of the hydrocarbon conversion
dramatically, especially at the inlet side of the
tube.
Methane reforming can be described as a
first-order reaction, irrespective of operating
pressure. At low temperature, the molecular dif-
fusion rate is much higher than the reaction ve-
locity so that, theoretically, the catalyst activity
can be fully utilized. If the temperature is high,
the conversion rate is determined by pore diffu-
sion, and catalyst efficiency is reduced. Hence,
large-surface catalysts offer an advantage with
regard to catalytic activity. For further details of
Gas Production 25
reaction mechanism and kinetics, see [12] and
[13].
Carbon Deposition. Carbon deposition is a
frequently experienced phenomenon with steam
reforming. Though generally various reactions
may cause solid carbon formation from car-
bon compounds containing gaseous phases [e.g.,
Boudouard reaction (2 CO
C + CO2 ), hy-
drocarbon decomposition (Cn Hm
n C + m/2
H2 ), the heterogeneous water gas reaction (CO +
H2
C + H2 O)], hydrocarbon decomposition
is practically the exclusive cause for carbon for-
mation in the course of reactions in the steam re-
forming process. Therefore carbon deposition is
observed mainly in the first half of the reformer
tubes where hydrocarbon concentrations are still
high and the approach to equilibrium low.
Investigations have shown [14] that the
thermodynamic limits of carbon formation
(graphite) do not apply below 700 ◦ C because
there the relevant reactions are dominated by ki-
netics. So the carbon-free area may increase, de-
pending on catalyst properties. Figures for a ura-
nium – nickel – α-alumina catalyst are given in
[15] and for a number of other catalysts in [13].
Figures 3 and 4 show experimental “equi-
librium constants” for the Boudouard reaction
and methane decomposition measured by vari-
ous authors, as well as calculated figures for ther-
modynamic equilibrium according to [16]. Fig-
ure 4 also depicts the “working line” for methane
steam reforming according to [17], by applying
two catalysts with different activities. Points on
the curves indicate the location of the measur-
ing point as a proportion of tube length (viewed
from the gas inlet).
In steam reforming of natural gas, the tem-
perature at the catalyst inlet is such that car-
bon might theoretically be deposited. This does
not occur, however, below ca. 650 ◦ C, but only
at higher temperature when an inactive catalyst
fails to decompose sufficient methane. Gener-
ally, the formation of carbon deposits is not in-
evitable even at operating temperatures where it
might be expected.
Figures 3 and 4 also illustrate the more fa-
vorable initial situation and possible further re-
forming of a naphtha-based rich gas with added
carbon dioxide (to obtain high-CO gases) if cata-
lyst activity remains unimpaired (line (c) in Fig.
26 Gas Production
3 or line (a) in Fig. 4) or if no further methane
conversion occurs (line (b) in Figs. 3 and 4).
Figure 3. Equilibrium constant of the Boudouard reaction
(2 CO
C + CO2 )
a) Condition of rich gas from naphtha at inlet to tubu-
lar reformer; b) Equilibrium reached for reaction (7)
only; c) Equilibria reached for reactions (7) and (8 a);
d) According to [14]; e) According to [13]; f) For nickel –
uranium catalyst according to [15]; g) For sulfided catalyst
according to [13]
Figure 4. Methane decomposition (CH4 → C + 2 H2 )
a) Equilibria reached for reactions (7) and (8 a);
b) Equilibrium reached for reaction (7) only; c) Equilibrium
constant for carbon in graphite form according to [16];
d) and e) Working lines for methane reforming in a reac-
tor tube; d) High-activity catalyst; e) Low-activity catalyst
with red hot tube section from ca. 650 ◦ C to equilibrium;
figures at the data points are proportions of tube length as
viewed from inlet; f) Equilibrium constant determined by
experiment according to [13]; g) Connecting line between
equilibrium constants determined by experiment at 410 and
525 ◦ C according to [14]
2.2.2. Catalysts, Catalyst Poisons,
Desulfurization
Steam reforming is generally carried out in the
presence of nickel catalysts. These catalysts are
usually in the form of thick-walled Raschig
rings, with 16-mm diameter and height and a 6 –
8-mm hole in the middle. However, especially in
modern steam reformers with high heat flux, cat-
alysts with high geometric surface (HGS-type)
are preferred. As already mentioned in Section
2.2.1, the access to the inner surface of catalysts
continuously decreases with increasing temper-
ature due to diffusion limitation. This is com-
pensated by introducing catalysts with a higher
surface to volume ratio. Typical shapes of this
type of catalysts are spoked wheels, gear wheels,
or rings with several holes. These catalysts are
additionally advantageous with regard to their
low pressure drop.
A general distinction is made between im-
pregnated and precipitated catalysts. The latter
are the more traditional types which are pro-
duced by coprecipitation of all constituents. Pre-
cipitated catalysts have a Ni-surface which is by
one order of magnitude higher than that of im-
pregnated catalysts and for this reason have an
excellent activity already at moderate temper-
atures. But they are more prone to sintering at
higher temperatures and do not have the mechan-
ical strength of supported catalysts.
Impregnated catalysts are manufactured by
separately impregnating a support with nickel
as the active constituent. The main advantage of
this type of catalyst is that the support can be cal-
cined at high temperatures before impregnation,
resulting in predetermined excellent mechani-
cal properties which are important especially
at high temperature application. As the condi-
tions of steam reforming have generally become
more severe, impregnated catalysts predominate
by far at present. Frequently used support ma-
terials are alumina (the α-modification is pre-
ferred today), magnesium oxide, or spinel type
substances (e.g., magnesium aluminum oxide).
In some cases, catalysts are stabilized by addi-
tion of a hydraulic binder (calcium aluminum
oxide). Crushing strength is decreased by the
hydration of magnesium oxide at low tempera-
ture (< 500 ◦ C) and by changes from the γ to

the α-modifications of alumina above 500 ◦ C.
A silicon dioxide content of < 0.3 wt % in the
catalyst is essential, because silicon dioxide be-
comes volatile in the presence of steam and may
foul the downstream heat exchangers through
which the reformed gas flows.
Nickel is at first present in the form of nickel
oxide; after the system has been heated, it is re-
duced in the reformer tube by hydrogen formed
when natural gas is added to steam. Some cat-
alysts require a special method of reduction for
which a definite steam: hydrogen ratio must be
maintained (see Fig. 5), according to [12] and
[13].
Figure 5. Reduction conditions for nickel oxide
Catalyst Poisons and Desulfurization. Cat-
alytic activity is affected seriously even by very
low concentrations of catalyst poisons in gases
to be reformed. Such catalyst poisons are sulfur,
arsenic, copper, vanadium, lead, and chlorine or
halogens in general. Sulfur, found in practically
all hydrocarbon feedstocks, in particular lowers
catalyst activity [18].
Earlier desulfurization systems used impreg-
nated activated carbon as adsorbent and oper-
ated at ambient temperature. However, because
their efficiency differs according to the particu-
lar sulfur compounds in the gas and because the
requirement with regard to the residual sulfur
content has increased, zinc oxide desulfurization
systems operating at 350 – 400 ◦ C are generally
preferred today. Iron-based adsorbents are used
in only a few cases where special conditions (i.e.,
low operating temperature, possibility of regen-
eration, sulfur composition) prevail.
Zinc oxide reactors are very reliable in ab-
sorbing hydrogen sulfide and, with limitations,
sulfur compounds such as carbonyl sulfide and
mercaptans. To achieve optimum desulfuriza-
Gas Production 27
tion conditions, certain space velocities and ef-
fective flow rates must be ensured. Sulfur pickup
ranges from 15 to > 30 %, that is almost com-
plete conversion of zinc oxide to zinc sulfide is
possible.
Organic sulfur compounds such as mercap-
tans and thiophenes require hydrogenation over
cobalt – molybdenum or nickel – molybdenum
catalysts. These catalysts are often arranged in
a separate vessel. Hydrogen or hydrogen con-
taining gas are added to the process feedstock
at temperatures of ca. 350 – 380 ◦ C. The or-
ganic sulfur compounds are converted to hydro-
gen sulfide and the corresponding saturated hy-
drocarbons. Hydrogen sulfide produced in the
hydrogenation stage is then absorbed by zinc
oxide. The hydrogenation reactor can be used
simultaneously to hydrogenate unsaturated hy-
drocarbons in the raw gas. This reaction is
strongly exothermic. Because the temperature
range for the hydrogenation stage is limited to
250 – 400 ◦ C, unsaturated hydrocarbon content
is limited as well. Ammonia, carbon monox-
ide, or carbon dioxide impurities in hydrogen
affect desulfurization and can lead to undesir-
able side reactions such as methanation [12]. An
economic solution particularly for natural gases
with low sulfur content is the combination of
hydrogenation and zinc oxide absorption. This
means that both catalysts can be combined in one
bed in the same reactor. Residual sulfur content
is normally < 0.2 mg/m3 [19].
2.2.3. Tubular Reformers
Tubular reformers are mostly top- and wall-fired
box-type units, apart from older types or special
designs (Fig. 6). Whereas in wall-fired reform-
ers, rows of reformer tubes are heated mainly by
the radiant side wall, top- or bottom-fired reform-
ers provide most of the heat through radiation of
the burner flame and the hot flue gases. Top-fired
reformers may, therefore, have several parallel
rows of tubes, whereas wall-fired reformers can
have only one row. Wall-fired reformers with a
large number of tubes consist of several units ad-
jacent to one another; waste heat from the flue
gases is recovered in a common system. Mod-
ern reformers in large plants that produce am-
monia and methanol synthesis gas from natural
gas contain hundreds of tubes arranged in rows.
28 Gas Production

Figure 6. Reformer types

A) Top-fired reformer; a) Inlet header(s); b) Pigtail; c) Burner; d) Catalyst-filled reformer tube; e) Flue-gas collector;
f) Refractory lined outlet manifold; g) Outlet pigtail; h) Outlet manifold
B) Wall-fired reformers; a) Inlet header; b) Flue-gas duct; c) Wall burners; d) Outlet manifold; e) Terraced wall; f) Burner

Firebox. The reformer box consists of sev- rameters such as jet diameter, fuel and air supply
eral layers of refractory insulation and insulating rates, and burner geometry produces a relatively
mats with an exterior metal skin. The hot face short, stable flame ca. 2 – 2.5 m in length; the
refractory must be resistant to temperatures > reformer tubes, therefore, receive their heat to
1200 ◦ C; the temperature is reduced to ca. 75 ◦ C a considerable degree from flue gas radiation.
on the outside of the metal skin. Accurate calculation of heat transfer requires a
Burner geometry, flame length and diameter, knowledge of flue gas backflow and flame emis-
tube-to-tube and row-to-row spacing, fired tube sion behavior.
length, and distance from the flame to the re-
former wall determine the homogeneity of heat
transfer to the tubes. Modern computers are
capable of linking up this reformer geometry
with heat-transfer processes inside the reformer
tubes (radial heat conductivity) to derive com-
plex equation systems from which heat trans-
fer at all points of the firebox can be calculated
(see Fig. 7). These equations yield local tem-
perature profiles for flame – flue gas (g – f), re-
former wall (d), tube wall (b), (c), reformed gas
(a) or catalyst, and local heat flux (e). These fig-
ures form the design basis for the reformer. If Figure 7. Approximate temperature profiles across a re-
the tube wall temperature and local heat flux are former
known, and heating and cooling rates are esti- a) Reformed gas (average over tube cross section); b) Tube
wall inside; c) Tube wall outside; d) Heater wall; e) Local
mated, the wall thickness of the reformer tubes heat flux; f) Flue gas; g) Flame
can be calculated.
One important factor is spacing between the
Flue gases are discharged via ducts inside the
reformer tubes, referred to as tube pitch. In cal-
firebox and cooled to ca. 200 ◦ C in heat exchang-
culating tube pitch, irregularities in heat flux
ers, which are used to preheat the gaseous feed-
around the tube must be considered [20].
stock, generate steam, etc.
Burners and Firing Systems. Top-fired re- Wall-fired reformers employ other burner de-
formers use turbulent open-jet burners with signs or flame shapes, such as resist burner cups
forced air supply. Appropriate selection of pa-

into which the fuel is burned or flames burning
parallel to the side wall.
Reformer Tubes. Normally, the tubes have
inside diameters of 75 – 125 mm, wall thick-
nesses of 10 – 20 mm, and fired lengths of 9 –
15 m, depending on reformer type (top- or wall-
fired). The fixed tube support is usually located
outside the firebox at the top or bottom; when
heated, the tube expands longitudinally from this
support. Counterweights or spring hangers often
relieve the tubes of ca. 50 % of their dead weight.
Tube wall thickness is calculated on the basis
of internal pressure and of 100 000-h creep-to-
rupture strength; see [20]. More sophisticated
calculations allowing for mechanical and ther-
mal stresses, and in some cases even establishing
a link between them, are being used increasingly
[21, 22].
Table 8 summarizes tube materials currently
preferred, along with their rupture strengths.
Tubes are welded to the required overall length
from centrifugally cast tube sections > 3 m in
length. The calculated “sound wall thickness”
must be increased by an allowance for fabrica-
tion tolerances.
The pressure drop inside a reformer tube de-
pends on the gas flow rate and geometry of the
catalyst; it is normally between 0.15 and 0.5
MPa.
Pressurized Convection Reformers. A ma-
jor factor determining the size of reformer tubes
is the pressure difference between the reformed
gas and the nearly pressureless flue gas. Obvi-
ously, the wall thickness of the reformer tubes
can be reduced if the pressure in the firebox is
increased. This concept is now mature enough
for application on an industrial scale [23]. Re-
former tubes with a much larger diameter than
usual can be employed; the catalyst is arranged
in an annular space, and reformed gas is recycled
internally by straight or helically coiled tubes (to
increase internal heat exchange). Such reform-
ers can be designed for hydrogen output up to
5000 m3 (STP)/h; beyond this, the wall thick-
ness of the pressure vessel makes the concept
economically unattractive.
Higher output can be achieved by connecting
several units in parallel. The pressurized com-
bustion reformer requires little space and can,
therefore, be prefabricated in modules. How-
Gas Production 29
ever, combustion air and off-gas from the PSA
unit required for the firing system must be com-
pressed to high pressure, whereas the flue gas
pressure energy can be recovered only partly in
expanders.
A promising route for the future might be to
increase process pressures to a level at which
compression of synthesis gas is no longer re-
quired [24].
Inlet Header and Outlet Manifold Sys-
tems. The preheated hydrocarbon: steam mix-
ture (400 – 530 ◦ C) is fed to the reformer tube
rows via inlet headers with branches to each in-
dividual reformer tube. These inlet pigtails are
designed to take up the expansion of the inlet
header and of the tubes (if the fixed support is un-
derneath the reformer), as well as their own ex-
pansion. Header and pigtails are made of carbon
steel (or alloyed carbon steel). Flexible metal
hoses are used instead of inlet pigtails only in
special cases.
Hot reformed gases are discharged from be-
low the catalyst supporting grid in the tubes to
outlet manifolds. The outlet manifolds are made
of centrifugally cast (see Table 8) or drawn mate-
rial (Incoloy 800 H). Brick-lined manifolds are
used as well; in this case, reformer tubes are
mounted directly on the manifolds or connected
by small-diameter straight tubes, or “flexitubes”
[25]. Another design has manifolds installed in
the bottom of the firebox; product gas is ex-
tracted through the reformer top by means of
one or more risers.
On leaving the outlet manifold, the hot re-
formed gases are cooled in heat exchangers
to generate steam or to preheat boiler feedwa-
ter, raw gas, etc. They are then fed to carbon
monoxide shift conversion units or carbon diox-
ide scrubbers for further conditioning.
2.2.4. Production of Fuel Gas and Synthesis
Gas
Operation of the reformer under defined reac-
tion conditions, in conjunction with additional
process steps, produces the desired gas compo-
sition for fuel gas or synthesis gas applications.
The variety of possibilities is indicated in Ta-
ble 9, which lists typical reaction parameters for
tubular reforming.
30 Gas Production
Table 8. Creep-to-rupture strength (average for minimum values) σRmin 100 000 for centrifugal castings, N/mm2
Material designation Trade names Temperature, ◦ C
(DIN 17 006)
800 850 900 950 1000 1050 1100
G-X 40 CrNiSi 2520 HK 40 25.0 18.0 12.0 8.0 5.0 3.0
G-X 35 CrNiSiNb 2424 IN 519 35.0 25.0 17.0 11.0 6.6
G-X 50 CrNiSiNb 3030 Märker RE30N 40.0 30.0 21.0 13.5 8.2 4.7 2.4
G-X 45 NiCrNb 3525 Pyrotherm G 35/25 NbTZ, KHR 35C 38.0 29.0 21.0 13.5 5.0 4.7 2.3
G-X 40 NiCrNbTi 3425 Manaurite XM 47.0 35.7 25.7 17.5 11.2 6.8 3.9
G-NiCr 48 W NA 22 H, Paralloy H48T 34.0 25.0 17.5 12.0 7.8 4.8 2.8
G-NiCr 50 Nb * IN 657 28.5 20.5 13.0 7.5 3.8
G-X 10 NiCrNb 3220 ** Pyrotherm G20 32Nb 27.0 18.0 11.0 6.4
* This material (which has good resistance to oil ash corrosion) is normally used as the hot face layer of centrifugally cast compound tubes;
the cold face is made of high-strength material.
** Material for hot but unheated outlet manifolds.

Table 9. Production of various types of gas by tubular reforming of gaseous hydrocarbons

Product gas for Typical process stages * Typical H2 O/C Typical pressure Typical
producing ratio, mol/mol at reformer tube reformed gas
outlet, MPa temperature,
(primary
reformer), ◦ C
CO desulfurization, tubular reforming with recycled CO2 , CO2 2–3 1–3 850 – 900
scrubbing, CO separation (e.g., low-temperature separation, CoSorb,
PSA, or membranes)
H2 desulfurization, tubular reforming, HT and LT conversion, CO2 4–5 1.5 – 3 800 – 900
scrubbing, methanation (standard arrangement)
desulfurization, tubular reforming, HT conversion, PSA, or 3 2 – 2.5 800 – 900
membranes
Oxosynthesis desulfurization, tubular reforming, CO2 scrubbing, partial separation 2.5 1–2 850 – 950
gas of hydrogen by PSA, addition of imported CO2 upstream of
reforming if necessary
Methanol desulfurization, tubular reforming, or additional secondary reformer 2.5 – 2.8 2–3 850 – 900 700 –
synthesis gas 800
NH3 synthesis desulfurization, tubular reforming (primary reformer), secondary 3.5 3–4 780 – 830
gas reforming, HT and LT conversion, CO2 scrubbing, methanation
Town gas desulfurization, tubular reforming, HT conversion, CO2 scrubbing 3.0 1 – 2.5 650 – 750
Reduction gas desulfurization, tubular reforming, or top gas recycling upstream of 1.25 – 1.5 0.65 0.2 – 0.3 0.15 – 850 – 1000 900
tubular reforming 0.2 – 1000
* PSA = pressure swing adsorption; HT = high temperature; LT = low temperature.

2.2.5. Special Reforming Processes
Reforming with Additional Carbon Diox-
ide. Reforming with additional carbon dioxide
is used to produce gases with an increased car-
bon monoxide content. By recycling carbon
dioxide from the reformer product gas, partially
or totally, the hydrogen: carbon monoxide ratio
can be adjusted in a range defined by the com-
position of the natural gas. By total carbon diox-
ide recycle the complete carbon content of the
process feed is converted to carbon monoxide.
In this case the shift conversion reaction (Eq.
7) is eliminated and the hydrocarbon conver-
sion follows exclusively Equation (8). Product
gases with particularly high content of carbon
monoxide are obtained by adding carbon dioxide
from an external source in addition to the carbon
dioxide recycle to the reformer feed. This com-
bined steam – carbon dioxide reforming entails
a greater risk of carbon deposits, which must be
countered by selecting appropriate reaction pa-
rameters and catalysts (see Section 2.3.3).
Whereas reduction gases having high hydro-
gen and carbon monoxide content are normally
produced by methane reforming with only a
slight amount of steam being added (< 1.5 mol
of steam per mole of methane), the Midrex pro-
cess in particular (direct reduction of iron oxide,
→ Iron, Chap. 2.6.1) relies heavily on combined
steam: carbon dixoide reforming.
Midrex Reforming. In the Midrex process,
iron ore reduction and the production of reduc-
tion gas are integrated. Natural gas is mixed with
off-gas from iron reduction (cleaned and humid-

ified gas from the direct reduction furnace). The
latter contains unreacted hydrogen and carbon
monoxide in addition to steam and carbon diox-
ide produced by oxidation of carbon monoxide
in the furnace. Typical for the process is a steam:
carbon ratio (regarding the molar carbon con-
tent of only methane and higher hydrocarbons)
of 0.65 and a carbon dioxide: carbon molar ratio
(see above) of ca. 0.8. Pressure at the reformer
outlet is ca. 0.2 MPa. Special catalysts (Midrex
and others) ensure that gases can be reformed
without carbon formation.
To this end, either catalysts of different ac-
tivities must be arranged successively in the re-
former tubes, or the activity of the catalyst must
be adjusted by means of a controlled sulfur con-
tent so that it will be lower at the tube inlet than at
the outlet. Reformed gas is conditioned prefer-
ably to a hydrogen: carbon monoxide molar ratio
of ca. 1.6. Processes for the production of direct
reduction gases are described in [26].
Steam Reforming with Addition of Air. In
the past, town gas was produced with addition
of process air to adjust gas density; examples are
the Koppers natural gas reforming process and
the Dr. Otto butane reforming process. However,
with the conversion of fuel gas systems to natural
gas, this technology has become less important.
It is still used to make synthesis gas for ammo-
nia production from low-boiling hydrocarbons
up to the naphtha boiling range in small com-
pact plants containing a combination of primary
and secondary reformers (see below).
Lately, natural gas reforming with addition
of air has been used temporarily to adjust gas
density during the changeover period from town
gas to natural gas until the conversion of gas ap-
pliances to natural gas is completed.
The standard technology for producing am-
monia synthesis gas from low-boiling hydrocar-
bons is the two-stage reforming process. The
first stage is catalytic steam reforming of hy-
drocarbons in a tubular reformer (primary re-
former). Product gas from the primary reformer,
which has a temperature of ca. 800 ◦ C, is then
reformed with air in an autothermal secondary
reformer at an outlet temperature of ca. 1000 ◦ C
(Section 2.5).
Methane Reforming with Nuclear or Solar
Energy. In high-temperature nuclear reactors,
Gas Production 31
recycled helium is heated from 350 to 950 ◦ C.
For catalytic reforming, hot helium is circulated
in indirectly heated heat exchangers in counter-
current to methane and steam flowing through
the reformer tube, releasing its sensible heat and
being cooled from 950 to 600 ◦ C. The preferred
reformer tube design has an inner helical tube
through which reformed gas is discharged to heat
the catalyst-filled tube; see [27, 28]. Such reac-
tors, termed EVA reactors, have been tested in
pilot plants since 1971 and are considered suit-
able for commercial reformed gas production.
Energy is supplied to the heating helium in the
core of a high-temperature nuclear reactor. In
CRS (i.e., Central Receiver System) solar plants,
this occurs in the receiver.
Reformed gas can be used to produce basic
chemicals (H2 , NH3 , CH3 OH) or, in conjunc-
tion with methanation, as a heat-transfer system
(ADAM – EVA Systems, see Section 5.3.4). No
known commercial applications have yet been
found.
2.3. Tubular Steam Reforming of Liquid
Hydrocarbons
In the mid-1950s, ICI initiated widespread use
of naphtha as feedstock for the steam reforming
process. This was enabled by the development
of special nickel catalysts in conjunction with a
very efficient naphtha desulfurization. Initially,
the ICI process was frequently used for town
gas production. Due to the abundance of natural
gas, naphtha reforming is meanwhile of minor
importance. Only at some locations with no ac-
cess to natural gas there is still some hydrogen
and syngas production based on naphtha.
Principles. Direct reforming of naphtha is
not generally different from natural gas reform-
ing. The conversion follows Equation (8) in the
same way as already described for the higher hy-
drocarbons contained in natural gas (see Section
2.2.1). Like natural gas reforming naphtha re-
forming is carried out in externally heated tubes
over a nickel catalyst and yields, via a complex
reaction mechanism, a gas mixture consisting
of hydrogen, carbon monoxide, carbon dioxide,
methane, and steam. The gas composition re-
flects the equilibria of Equations (8 a) and (7) at
32 Gas Production
outlet conditions. If less active or partially deac-
tivated catalysts are used, the equilibrium con-
centration of methane (as per Eq. 8 a) is not at-
tained, and the methane content of the reformed
gas is higher than at equilibrium. Due to the
higher carbon content in the process feed naph-
tha reforming results in a product gas with in-
creased carbon monoxide (and dioxide) content
compared to natural gas feed.
2.3.1. Commercial Processes
A mixture of desulfurized and evaporated naph-
tha with superheated steam (molar steam: car-
bon ratio 3: 1 or higher) is supplied to reformer
tubes at 450 – 550 ◦ C.
Catalyst. Due to the high carbon: hydrogen
ratio in the feedstock naphtha direct reforming
is characterized by an increased tendency of car-
bon formation. This is mainly caused by naph-
tha cracking and dehydrogenation reactions, es-
pecially on acidic centers of catalysts based on
alumina which is the most frequently used sup-
port material. The breakthrough of naphtha re-
forming has been enabled by the development
of alkalized catalysts. The acidic centers of the
support are neutralized by adding potassium to
suppress naphtha cracking. Moreover, the steam
conversion of carbon once formed by naphtha
cracking is strongly enhanced by the presence
of potassium. However, alkali also delays com-
plete reforming to carbon monoxide and hydro-
gen. Therefore, the portion of the reformer tube
that is filled with potassium-laden catalyst is re-
stricted to the minimum required for reliable
naphtha conversion; the rest of the tube is filled
with more active alkali-free catalyst.
Today, a controlled continual release of
potassium is achieved by incorporating a special
potassium compound (KAlSiO4 ) in the catalyst,
thereby reducing the potassium vapor pressure
[12]. Alternatively, alkali-free catalysts mostly
based on magnesium oxide are used.
Desulfurization. Naphtha generally con-
tains organic sulfur compounds, and the sulfur
content may be as high as several hundred parts
per million. It must, therefore, undergo hydro-
genating desulfurization with hydrogen at 350
– 400 ◦ C. Cobalt – molybdenum catalysts or, if
gases with a certain carbon oxide content are
intended for hydrogenation, nickel – molybde-
num catalysts are used. The sulfur converted to
hydrogen sulfide is then adsorbed on zinc ox-
ide, which has been used commercially as a hot
desulfurization agent since the 1940s.
2.3.2. Fuel Gas and Synthesis Gas from
Liquid Hydrocarbons
The description given in Section 2.2.4 and Ta-
ble 9 applies analogously to the production of
gas from naphtha. These plants are distinguished
from those based on natural gas by the following
features:
1) More complex desulfurization systems;
2) Use of a special catalyst in the tubular re-
former and, in conjunction with this, a special
start-up system;
3) Fewer reformer tubes per quantity of hydro-
gen and carbon monoxide produced at equal
heat loads per unit area (natural gas requires
considerably more reforming energy than hy-
drocarbons in the naphtha boiling range); and
4) Larger carbon dioxide washing systems
(naphtha has a higher carbon content than
methane).
Details of modern integrated ammonia plants,
particularly the steam system, are described
elsewhere (→ Ammonia) [9].
In town gas production by the ICI process, the
reformed gas is produced with a heating value
below that of town gas. The calorific value of the
reformed gas must, therefore, be increased
1) By adding low-boiling hydrocarbons (e.g.,
LPG) and
2) By producing gases with a higher calorific
value in special process stages for addition
to the reformed gas. This has been achieved
by means of a downstream gas recycle hy-
drogenator (GRH) or a parallel rich-gas stage
based on naphtha (see Section 2.4), or by re-
acting reformed gas from the tubular reformer
with additional naphtha and steam in a sec-
ondary reformer [29].
2.3.3. Special Processes
Steamless Carbon Dioxide Reforming.
Feedstocks with high carbon: hydrogen ratios

(such as naphtha) and low steam: carbon ratio
favor the production of synthesis gas with high
carbon monoxide and low hydrogen content (as
required, for instance, for the oxo synthesis). In
practical applications, however, this system soon
reaches the point at which carbon formation oc-
curs, particularly at high pressure. This difficulty
has until now been overcome by reforming the
gases under established process conditions (i.e.,
CO2 recycling with less steam than in regular
steam reforming), washing out carbon dioxide,
separating hydrogen and carbon monoxide in
a cryogenic or PSA unit, and finally remixing
them in the desired ratio. In this concept unde-
sirable hydrogen surplus can often be used only
to fire the reactor.
The hydrogen production can be minimized
by converting hydrocarbons only with carbon
dioxide according to the reactions
CH4 +CO2
2 CO+2 H2
or as example for higher hydrocarbons
C3 H8 +3 CO2 → 6 CO+4 H2
This leads to hydrogen: carbon monoxide ra-
tios of 1: 1 or even less.
Steamless carbon dioxide reforming requires
still more sophisticated conditions and catalysts
than naphtha direct reforming [30]. It has been
realized in the Calcor C process that employs
special catalysts and ambient or only slightly
elevated pressure. This system recovers the nec-
essary carbon dioxide from the reformed gas in
a monoethanolamine (MEA) or diethanolamine
(DEA) wash unit, recycles it to the reforming
stage, and adds imported carbon dioxide as re-
quired [31].
Downstream of the reformer and carbon diox-
ide wash unit, raw gas from a C3 – C4 feed-
stock, for example, will contain hydrogen and
carbon monoxide at a ratio of ca. 0.65, with a
methane content below 1 vol %. For higher car-
bon monoxide concentrations, ranging to > 99.5
vol %, carbon monoxide and hydrogen are sepa-
rated in a PSA unit or cold box. Plants designed
for 160 and 250 m3 (STP) of carbon monoxide
per hour have been constructed to date.
Higher Feedstocks. Catalytic reforming of
hydrocarbons with a higher boiling range has of-
ten been investigated. In most cases, only short-
term tests were made, which did not reach the
Gas Production 33
stage of commercial application. The use of very
high-boiling hydrocarbons is described in [32].
In other tests, naphtha, crude oil, and heavy
residues have reportedly been converted to re-
formed gases with a hydrogen content of ca.
60 – 65 % without desulfurization or removal of
heavy metals [33]. The alternative of noncat-
alytic conversion of high boiling hydrocarbons
or even residues and the high availability of nat-
ural gas have slowed down the interest in these
feedstocks at present.
2.4. Prereforming
Prereforming is a term which has been intro-
duced into common nomenclature of gasifica-
tion processes in the 1980s. In the most used
sense it means the application of an adiabatic
low temperature steam reforming step upstream
of a conventional steam reformer using natural
gas as feedstock. Regarding effect and condi-
tions this process step corresponds to the steam
conversion of naphtha in the so-called rich gas
process which has been applied for nearly 40
years. Even the same or very similar catalysts
are used [34].
Prereforming can be defined as a steam re-
forming process at limited temperatures (<
700 ◦ C) resulting in an intermediate product gas,
the main compound of which is methane besides
steam. The process is in thermodynamic equilib-
rium with respect to the methane (Eq. 8 a) and
shift conversion reaction (Eq. 7). The product
does not contain higher hydrocarbons. Normally
this intermediate gas is further processed in a
steam reformer, but in special cases it can also
be used for other applications, particularly for
the production of fuel gas (e.g., town gas, SNG).
2.4.1. Principles
Prereforming follows the same sequence of re-
actions as tubular steam reforming characterized
by Equations (8), (8 a), and (7). But in contrast
to the latter, the equilibrium is established at far
lower temperatures. The main feature of prere-
forming is the irreversible, complete conversion
of the higher hydrocarbons fed to the process.
Due to the comparably low temperature the main
compound of the product gas is — besides un-
converted steam — methane. For this reason the
34 Gas Production
steam conversion of naphtha is called “rich gas
process”, which reflects the fact that the result-
ing product gas is rich in methane. The remain-
ing compounds are hydrogen, carbon dioxide,
traces of carbon monoxide, and the inerts con-
tained in the feed.
Depending on the feedstock prereforming
can be endo- or exothermic. Generally the steam
conversion of hydrocarbons to carbon oxides
and hydrogen is endothermic. But as prereform-
ing is carried out at only moderate temperatures,
the carbon oxides are further converted to meth-
ane, a reaction that is highly exothermic. So, if
naphtha is used as process feed, prereforming is
exothermic whereas in the case of natural gas,
the main compound of which is already meth-
ane, the overall reaction is endothermic.
2.4.2. Catalysts
As prereforming is a steam reforming process
at low temperatures, special catalysts are re-
quired to achieve sufficiently high reaction rates.
Common properties of these catalysts are a high
nickel content (30 – 70 wt %) and a high spe-
cific surface (e.g., 200 m2 /g); the support mate-
rial may be made, for instance, of alumina with
minor additions of potassium or magnesium sil-
icate. The geometric form is also adjusted to
the special requirements among which the con-
version of higher hydrocarbons is the most im-
portant. To restrict diffusion ways small pellets
(e.g., 5 × 5 mm tablets) are generally used.
Because of the lower temperature, prereform-
ing catalysts are still more sensitive to poison-
ing than conventional steam reforming cata-
lysts. This is especially true for sulfur poison-
ing, which is at least partly reversible at the
higher temperature level of tubular steam re-
forming, but irreversible at prereforming con-
ditions. For this reason special care has to be
taken in the desulfurization step, the residual sul-
fur content of which should not exceed 0.2 mg
per kilogram of gas. Naphtha is desulfurized by
using the refinery-proven technology of hydro-
genating desulfurization (see Section 2.2.2).
2.4.3. Prereforming of Natural Gas
Of the different variations of this process, pre-
reforming of natural gas is most frequently used
at present. Driving force for the application of
this technology is the general constraint for in-
creased economy.
The prereformer is installed upstream of the
tubular steam reformer to ease its operation. As
all higher hydrocarbons contained in the natural
gas are converted, the risk of carbon formation,
which is the most critical point in steam reform-
ing, is considerably lowered. This allows the de-
crease of the steam: carbon ratio and an increase
in the heat load on the reformer tubes, which
means less energy consumption and smaller
equipment. In addition hydrogen is produced
by partial conversion of natural gas and further-
more residual traces of catalyst poisons are ab-
or adsorbed in the prereformer. This gives, ef-
fectively, a catalyst of optimum activity at the
inlet of the tubular reformer, where high activity
is required most.
Prereforming is generally carried out in adia-
batic reactors with a typical inlet temperature
close to 500 ◦ C. Due to endothermic hydrocar-
bon conversion the outlet temperature is lower
by 25 to 40 ◦ C, depending of the content of
higher hydrocarbons in natural gas. Figure 8
shows a characteristic temperature profile of an
adiabatic prereformer.
Figure 8. Characteristic temperature profile in a natural gas
prereformer
a) Fresh catalyst; b) Spent catalyst
An option that is frequently made use of in
prereforming is the reheating of prereformed gas

Figure 9. Tubular steam reforming with prereformer and reheating of prereformed gas
a) Prereformer; b) Reformer tube; c) Furnace; d) heat recovery
before feeding it to the steam reformer. As steam
reforming technology generally has a surplus of
thermal energy which can only be utilized for
steam generation, this is an additional possibility
to improve the overall energy efficiency of a gas
production plant. In conventional steam reform-
ing the reintegration of available process heat ei-
ther from flue or from product gas is restricted by
the risk of cracking, that may occur when heat-
ing natural gas – steam mixtures to temperatures
above ca. 550 ◦ C. This risk depends essentially
on the content of higher hydrocarbons. Due to
the absence of hydrocarbons except methane and
the increased hydrogen content, prereformed gas
can be reheated to 650 ◦ C without any problem
(Fig. 9).
An alternative to adiabatic operation is carry-
ing out prereforming in heat exchanger type re-
actors by supplying heat from an outside source.
This source can be the product gas of the down-
stream main reformer (steam reformer or sec-
ondary reformer) or the flue gas of the firebox
of the steam reformer. In this case the outlet tem-
perature of the prereformer can be up to 700 ◦ C.
By this arrangement even more available sensi-
ble heat can be reintegrated in the process than
by reheating.
2.4.4. Prereforming of Naphtha; Rich Gas
Process
The rich gas process is the traditional implemen-
tation of prereforming. In addition to prereform-
ing in its actual sense this process has been used
Gas Production 35
particularly for the production of fuel gases dur-
ing the decades of its application.
Development of the rich-gas (high-methane
gas) process started in England in the mid-1950s
[35]. Parallel developments took place in Ger-
many and Japan from about 1960. Today, the
commercially available processes are those of
British Gas, BASF – Lurgi, and Japan Gasoline.
Initially, the process was used mainly for
the production of town gas. Soon its advan-
tages were also applied to the production of
high-carbon monoxide synthesis gases. In the
early 1970s, the rich-gas process was used in
the United States to produce substitute (or syn-
thetic) natural gas (SNG).
The rich gas process is carried out commer-
cially at 350 – 550 ◦ C and 1 – 5 MPa. The out-
let temperature of a rich-gas reactor is ca. 30
– 100 ◦ C higher than the inlet temperature of
the hydrocarbon/steam mixture. Like with pre-
reforming of natural gas the composition of the
rich gas can be calculated from the equilibrium
constants of the reversible reactions (Eqs. 8 a, 7)
according to [36] (see Fig. 10).
The sequence of reactions occurring typically
in an adiabatic shaft reactor can be observed by
following the temperature profile. At the inlet
of the catalyst bed the temperature profile is at
first determined by endothermic cracking and
gasification reactions, which cause the temper-
ature to drop by ca. 20 ◦ C. Further in the course
of the reaction, exothermic hydrogenation reac-
tions prevail, leading to a temperature increase
of ca. 60 ◦ C above inlet temperature (Fig. 11).
36 Gas Production
Figure 10. Equilibrium composition of rich gas C: H = 6;
2.0 kg H2 O per kilogram naphtha
a) 2.5 MPa; b) 4.0 MPa; c) 5.5 MPa
Figure 11. Characteristic temperature profile in a rich gas
reactor
During operation, the temperature profile
moves through the catalyst bed to the gas out-
let. When the upper temperature point (i.e.,
the end point of the temperature increase) ap-
proaches the end of the catalyst bed, naphtha
breaks through. Depending on the downstream
reaction stage (e.g., tubular reformer or metha-
nation), naphtha breakthrough can be tolerated
only up to a certain concentration.
Migration of the temperature profile is caused
by exhaustion or blocking of the active nickel
centers because of recrystallization, polymer de-
posits, or catalyst poisoning (sulfur, chlorine, ar-
senic, etc.). If caused by polymer deposits, this
profile migration can be reversed to some extent
by regenerating with steam or hydrogen.
Three processes have predominated commer-
cially in the past:
BASF – Lurgi Process. This process is used
commercially for the production of town gas,
high-carbon monoxide synthesis gas, carbon
monoxide, hydrogen, and SNG. The first com-
mercial plants have been in operation since 1965
[37].
This process uses a relatively stable rich-gas
catalyst which is fully active as low as 400 ◦ C.
Another characteristic of this process is the pre-
ferred use of indirectly heated naphtha evapora-
tors.
CRG Process. The catalytic rich-gas (CRG)
process is based on developmental work by F.
J. Dent (Midland Research Station of the Gas
Council). The process was used mainly for pro-
ducing town gas and SNG over a nickel cata-
lyst on an alumina carrier material. The temper-
ature profile moves almost unchanged through
the entire CRG catalyst bed. The first commer-
cial plants have been in operation since 1965
[36].
MRG Process. A special feature of the
methane rich-gas (MRG) process is the use of
a selective hydrogenation catalyst in the hydro-
genating naphtha desulfurization stage, which
is capable of operating with hydrogenation gas
having a low hydrogen content [38].
Substitute Natural Gas (SNG). The first
commercial plants for production of SNG were
built in the United States. They use a rich-gas

reactor, generally followed by two methanation
stages, carbon dioxide washing, and gas drying.
Steam: naphtha ratios of 2.0 kg/kg or slightly
higher are applied. An improvement was the in-
stallation of a second rich gas stage after the first
one. To the second rich gas stage only naphtha
is added (in about the same proportion as to the
first rich gas stage) or naphtha and only a small
amount of steam. Thus, the overall steam: naph-
tha ratio decreases to ca. 1.1 – 1.4 kg/kg. The
temperature range of the second stage varies
according to the process. The usual inlet tem-
perature is 350 – 380 ◦ C; the outlet temperature
is about 100 ◦ C higher. The two-stage mode
lowers steam consumption (i.e., increases effi-
ciency) and the amount of steam to be condensed
downstream. It improves the rich gas composi-
tion by decreasing the hydrogen content after
the second rich gas stage.
Usually, rich gas from the rich-gas stage(s) is
cooled to ca. 300 ◦ C and methanated in a shaft
reactor under adiabatic reaction conditions by
using nickel catalysts. Because undecomposed
residual steam in the rich gas is present dur-
ing this reaction, the process stage is termed wet
methanation. After cooling and steam conden-
sation, the methane content can be increased fur-
ther in a second methanation stage (dry metha-
nation). The dry methanation stage can be ar-
ranged upstream or downstream of the carbon
dioxide scrubber (see Section 5.3.3).
The possibility of multistage rich-gas produc-
tion and multistage methanation offers a great
variety of combinations and process alternatives
for SNG production. Figure 12 shows the over-
all diagram of an SNG plant with combined
two-stage rich-gas production and single-stage
methanation.
Town Gas. The rich-gas process was origi-
nally used for town gas production. The stan-
dard production concept of town gas from naph-
tha, with total conversion of naphtha in a rich-
gas stage followed by partial reforming of the
rich gas in an externally heated tubular reformer
to yield a hydrogen-rich gas (see Fig. 13), was
developed quite early. Hydrogen-rich reformed
gas from the tubular reformer is treated further
in the usual manner (CO shift conversion, CO2
scrubber, etc.).
The ICI method of injecting evaporated meth-
anol into town gas upstream of the high-tempe-
Gas Production 37
rature conversion stage has been applied in some
town gas plants as an elegant way of increasing
capacity to cover peak requirements in winter.
This has enabled the capacity of existing plants
to be increased by 20 – 30 %.
Methanol can be converted to town gas in
a rich-gas stage. However, in view of the com-
paratively high price of methanol, this is eco-
nomically justifiable only for covering peak re-
quirements in winter. Although capital invest-
ment costs for the plant are low, the process has
found only limited application.
2.5. Autothermal Catalytic Reforming
Catalytic reforming with air or oxygen has been
in use longer than either tubular reforming or
partial oxidation. Representatives of this first
generation technology are the ONIA-GEGI and
the SEGAS processes, both used for the pro-
duction of fuel (town) gas. Feedstock in these
cases was gas oil or even crude oil, resulting in
a high deactivation rate of the catalysts in use by
coking. Correspondingly these processes were
operated discontinuously with periodic regener-
ation. Plant designs today, however, differ sub-
stantially from this type of plant, as target prod-
uct (syngas) as well as feedstock (natural gas)
have changed completely and continuous oper-
ation is a “must”.
Characteristic for autothermal reforming is
the high flexibility of the process. This generally
enables a wide range of reaction conditions with
regard to feedstock, steam: carbon ratio, tem-
perature and pressure. Typical operating condi-
tions are outlet temperatures close to 1000 ◦ C
and pressures between 3 – 4 MPa. Suitable feed-
stocks are natural gas, LPG, and naphtha up to
a boiling end point of ca. 200 ◦ C. Furthermore
autothermal reformers are often fed with gases,
which have already passed a steam reformer
(“primary reformer”). In this case, the autother-
mal reformer is called “secondary reformer”. To-
day, the combination of tubular steam reforming
and autothermal reforming is the standard tech-
nology for the production of ammonia synthesis
gas. Autothermal reforming is more flexible than
tubular reforming because the higher allowable
operating temperature can compensate for any
increase in methane slip which higher pressure
would otherwise cause. Furthermore, the higher
38 Gas Production

Figure 12. SNG plant

a) Desulfurization; b) Rich gas reactor; c) Hydrogenating gasification stage; d) Methanation; e) CO2 wash

Figure 13. Diagram of a town gas plant operation on the rich gas process based on naphtha
a) Desulfurization; b) Rich gas reactor; c) Tubular reformer; d) HT conversion; e) Naphtha evaporator; f) CO2 wash

operating temperatures can also compensate for
a wider equilibrium approach (difference bet-
ween actual and equilibrium temperature at the
reactor outlet) which may be caused by mild sul-
fur poisoning of the catalyst. The maximum op-
erating temperature is not limited by the tube
material, as in tubular reformers, but only by the
stability of the catalysts and the refractory lining
of the reactor.
Oxidizing agents may be oxygen or air. The
selection depends on whether the presence of
nitrogen in the reformed gas is desirable, e.g.,
for the production of ammonia. By proper par-
tition of primary reforming and secondary re-
forming with air, a final syngas with stoichio-
metric hydrogen: nitrogen ratio is obtained. The
application as secondary reforming in ammonia
synthesis is by far the most frequent commercial
application of autothermal reforming.
There are two versions of the process differ-
ing in reactor design and arrangement of the cat-
alyst bed. In one type of reformer the reactants
(feedstock, steam, and oxygen or air) are dis-
charged directly from a mixer to the catalyst in
a fixed bed reactor. In the second type the mixer
acts as a burner discharging into an empty, usu-
ally conical space above the catalyst bed, which
only fills the lower portion of the reactor. The
latter modification has generally proven as the
more versatile and is used predominantly.
Typical applications of the two versions of the
process are compared in Table 10. A methane tail
gas was selected as feedstock for the all-catalytic
version, whereas reformed gas from a tubular re-
former for the production of ammonia synthesis
gas (typical use of a secondary reformer) was
employed for the version with precombustion.
 Gas Production 39
Table 10. Data for two reformed gases obtained by autothermal
reforming
the danger of bypass streams between lining and
Methane tail gas Reforming with
pressure vessel, which can lead to overheating
reforming with air addition and (see Fig. 14). In one frequently used modifica-
oxygen addition precombustion tion the reformer is provided with a water jacket
(secondary
reformer) that generally cools at atmospheric pressure but
Gas for reforming occasionally is slightly pressurized.
Composition, vol %
CO2 7.11
CO 3.90 4.25
H2 1.80 34.32
CH4 80.00 3.90
C2 H 4 0.25
C2 H 6 0.05
N2 1.70
Ar 12.30
H2 O 50.42
Flow rate, m3 /h 55 000 160 000
Pressure, MPa 3.0 3.04
Temperature, ◦ C 500 780
Oxygen or air
Flow rate, m3 /h 27 725 30 400
Temperature, ◦ C 240 550
Steam
Flow rate, kg/h 113 200
Temperature, ◦ C 485
Reformed gas (dry)
Composition, vol %
CO2 13.23 10.59
CO 16.99 11.67
H2 63.23 55.52
CH4 1.08 0.19
N2 0.65 21.77
Ar 4.82 0.26
Flow rate, m3 /h 148 400 109 000
Reformed gas (moist)
Flow rate, m3 /h 251 450 196 000
Pressure, MPa 2.65 2.97
Temperature, ◦ C 925 965

The catalysts used consist of thick-walled

Raschig rings 16 mm in diameter and height,
having a hole of 6 – 8 mm in the middle (stan-
dard size). The nickel content is about 3 –
12 wt %. Aluminum oxide (preferably the α-
modification) is used as carrier material, and the
content of silicon dioxide should be < 0.2 % be-
cause of its volatility with steam.
Figure 14 shows the design of a modern Figure 14. Autothermal reformer (secondary reactor)
a) Burner; b) Refractory lining; c) Water jacket; d) Catalyst;
commercial autothermal reformer. The refrac- e) Grid
tory lining is almost always multi-layered; high-
strength bricks or other lining materials (casta- The catalyst grid is usually made of heat-
bles) are used on the hot face, whereas mate- resistant refractory material. Catalyst can be re-
rials of lower bulk weight and high insulating moved by suction from the top.
capacity are used on the cold face (inner wall of The burner (mixer) is the most critical part of
pressure vessel). Special attention must be paid the autothermal reformer. This is true for both
to ensuring a close fit between lining and pres- types of reactor design. In most cases, the burner
sure vessel (vapor stops), because the consider- is designed as a single-tube mixer. Various types
able pressure drop in the catalyst bed involves of burner nozzles are available, all intended to
40 Gas Production
produce a homogeneous mixture of the oxidant
(oxygen or air) and the gasification agent before
they enter the catalyst bed. The burner internals
are made of highly heat-resistant steel or cast
steel; some burner types are cooled.
To achieve sufficient mixing of the differ-
ent inlet gas streams is a special problem in the
flameless version of the process, because a cer-
tain free space below the mixer is required. As
linear gas velocities have to be high in this area
to avoid ignition, the mechanical stress on the
catalyst is high, leading to abrasion and disin-
tegration. This effect causes an increase in the
empty space below the mixer that has to be com-
pensated for by periodical refilling of catalyst
during operation which is difficult to perform.
The advantage of this operation mode is that the
maximum temperature in the reactor does not
essentially exceed the adiabatic end temperature
(reactor outlet temperature).
In the open flame version of autothermal re-
forming generally a good mixture of the feed
gases is achieved. The problem to be solved in
this case is to keep the flame, which has temper-
atures even in excess of 3000 ◦ C, away from
the reactor wall and the catalyst surface. An
enormous progress has been made in the last
years by applying model calculations (Compu-
tational Fluid Dynamics) for burner and flame
[39]. Therefore, this modification of autother-
mal reforming has become the clearly superior
technology.
Besides ammonia synthesis — where au-
tothermal reforming (secondary reforming) is
standard technology — and a specific applica-
tion in the gasification of Fischer – Tropsch tail
gas, autothermal reforming is also applied in
some large-scale methanol plants. The syngas
production in these cases follows the mode of
“combined reforming”, a combination of tubu-
lar steam reforming and autothermal reform-
ing comparable to ammonia syngas production.
Combined reforming enables the production of
a syngas with an optimum ratio of hydrogen to
carbon oxides and minimizes the feed gas con-
sumption in this way. However, pure oxygen is
required as oxidant. This requires additional in-
vestment cost, if the oxygen has to be produced
on site. Therefore combined reforming is eco-
nomical particularly for large-size plants with a
capacity above 1000 t/d (see Section 7.1).
As already stated, a main advantage of au-
tothermal reforming is the “cold” shell of the
reactor, which allows the application of high re-
action temperatures and pressures. Whereas a
temperature close to 1000 ◦ C is already a cer-
tain limit in view of the heat resistance of the
used catalysts, the potential of applying higher
pressures is not yet finally utilized. Pressures up
to 8 MPa, usual in noncatalytic partial oxida-
tion, seem to be possible also for the catalytic
version and will make it increasingly attractive
in the near future. The design of a plant with
one pressure level for syngas production (only
autothermal reforming) and methanol synthesis
has been patented.
3. Noncatalytic Partial Oxidation
and Special Gasification Processes
for Higher-Boiling Hydrocarbons
3.1. Raw Materials
Partial oxidation is the most commonly used
process for gasification of heavy oil although
virtually all hydrocarbon mixtures regardless of
origin, are suitable feedstocks.
Crude Oil, Crude Oil Distillates and Resid-
ual Oils. Crude oil (→ Oil Refining) is a mix-
ture of many different types of hydrocarbon.
These can be classified in one of three ways: as
alkanes, (and isoalkanes), naphthenes, and aro-
matics; by the number of carbon atoms in the
molecule; or by their boiling point, which is ap-
proximately proportional to this number. How-
ever, crude oils also contain varying quantities
of other substances, which also play a role in the
usability of the oil and, especially, of the residue.
The most important impurities are sulfur com-
pounds; others are oxygen- and nitrogen-bearing
components, as well as minerals (sand and dis-
solved salts).
In addition, some impurities not naturally
present in the crude stem from its transporta-
tion; the main example is water, usually seawa-
ter with a high salt content. Residual oils may
also contain impurities that arise from wear of
catalyst, refractory material, and equipment in
conversion units.
As a general rule, low-boiling components
are distilled from the crude oil and marketed as

light naphtha, heavy naphtha, kerosene, and gas
oil. However, some crudes contain only small
amounts of light ends; the extremes are plastic
asphalts (→ Asphalt and Bitumen). These re-
sources, from which marketable products can
be obtained only by applying expensive refining
techniques, are suitable as feedstocks for par-
tial oxidation with practically no pretreatment,
except removal of water, salts, or solids.
Crude oil distillates in the boiling range of
ca. 35 – 360 ◦ C are valuable raw materials for
the chemical industry and are also processed into
motor fuels or used as light fuel oil. Like crude
oil, these distillates are used for gas production
only in special cases, for example, if a surplus
of various distillates cannot be balanced out in
the refineries.
The gas recycle hydrogenator (see page 51),
in which only hydrocarbons with a final boiling
point ≤ 325 ◦ C can be gasified, is an example
of the way in which process considerations can
restrict feedstock suitability.
Residual oils are the preferred raw material
for partial oxidation. First, they are generally
cheaper than distillates; second, the percentage
of residues that cannot be used for combustion
purposes is increasing because of pollution con-
trol. For example, in some places, power stations
are only permitted to burn heavy oils with a sul-
fur content < 0.8 %.
Refinery technology, too, contributes greatly
to the increasing quantity of high-boiling, high-
sulfur residues. To recover an ever-increasing
proportion of light and middle distillates from
crude oil, processes have been developed that
also enable recovery of naphtha and gas oil
from distillation residues. Among these pro-
cesses are liquid-phase cracking (→ Oil Refin-
ing, Chap. 3.2), catalytic reforming (→ Oil Re-
fining, Chap. 3.4), solvent deasphalting (→ Oil
Refining, Chap. 3.6), and hydrocracking (→ Oil
Refining, Chap. 3.5). In some cases, the residue
from these processes may even be solid coke;
it contains practically all the impurities in crude
oil, apart from those sulfur compounds that have
already been driven off during distillation and
salt from seawater, which is removed beforehand
in the desalter.
On assessing the suitability of residual oils
for gasification, the quantity and type of ash,
feedstock viscosity, and above all, the ratio of
alkalis to vanadium which is important for the
Gas Production 41
lifetime of the refractory lining must be consid-
ered. Properties such as boiling range, carbon –
hydrogen ratio, and sulfur content do not influ-
ence suitability but are important for assessing
design parameters. Some typical residual oils
and other feedstocks currently used for partial
oxidation are listed in Table 11.
Other Feedstocks. In addition to crude oil
and its manifold products, a number of other
hydrocarbon mixtures, as well as carbon- and
hydrogen-rich compounds, are used for gasifi-
cation of heavy oils. Chief among these are cer-
tain liquid byproducts from coal gasification and
upgrading.
In gasification of bituminous coal by the
Lurgi pressure gasification process (see Section
4.4) aqueous condensates as well as medium oils
and coal tar are obtained as byproducts. Medium
oils have a variety of uses, but the generally fluid
tar can only be recycled to the gasification reac-
tor or used as a feedstock for heavy-oil gasifica-
tion. Precleaning, at least by settling, is neces-
sary because of the generally high ash content
of the tar, which may be as much as 15 %.
Lignite tar oil is a byproduct of the car-
bonization of lignite or lignite briquettes. Like
coal tar, it may contain a larger or smaller quan-
tity of dust, depending on the nature of the raw
material and the characteristics of the carboniza-
tion process. Carbonization of lignite is uneco-
nomic today. However, certain plants are still
operated; in some cases, the char and lighter
condensation products are sold and the lignite
tar oil is used as a feedstock for gas production
by partial oxidation. In gasifying coal and lig-
nite tars, attention must be paid to the content
of low-melting ash, which may require slagging
operation.
In a few cases, undesirable or unsalable
byproducts of synthesis processes are used for
partial oxidation, preferably when the gas pro-
duced by oil gasification is suited to such synthe-
sis processes. An example of this is oxo synthe-
sis, in which oxo alcohols and various byprod-
ucts are produced from propylene and carbon
monoxide: hydrogen mixtures. One of these by-
products is isobutyraldehyde, which is formed
in considerable quantities. It has already been
used for partial oxidation with great success.
The heavy products of tar sand extraction (→
Tar Sands) and oil shale retorting (→ Oil Shale)
42 Gas Production
Table 11. Specific data for typical feedstocks (basis: Lurgi oil gasification, gasification pressure: 6 MPa; no soot recycle)
Feedstock type
Feedstock properties Natural gas Vacuum Propane Petroleum Orimulsion a
residue asphalt coke (35 % (29 % water)
water)
Specific gravity (15 ◦ C) 1.05 1.14 1.03 1.002
Kinematic viscosity, m Pa · s 180 620 150 300
at ◦ C 200 200 80 20
C/H ratio, kg/kg 3.01 8.72 9.02 26.65 8.88
S content, wt % 4.1 6.1 3.4 4.00
V content, mg/kg 210 280 1000 300
Ni content, mg/kg 70 120 220 50
Na content, mg/kg 30 40 20 – 120 80
Ash content, wt % 0.07 0.12 0.05 0.03
Higher heating value HHV (dry), MJ/kg 53.32 39.82 39.65 42.63 42.84
Feed flow rates, kg per 1000 m3 (STP) b
of CO + H2
Hydrocarbon 286 360 372 426 368
Oxygen c 338 378 387 416 403
Steam (380 ◦ C) 126 173 20 16
Gasification mode boiler boiler boiler quench quench
Product gas composition, mol % (dry)
H2 62.0 45.4 44.0 32.9 43.9
CO 33.5 49.1 48.5 58.0 48.7
CO2 3.1 3.9 4.5 5.9 4.8
CH4 0.8 0.3 0.2 0.2 0.2
N2 + Ar 0.6 0.2 1.3 1.4 1.4
H2 S 1.0 1.4 0.9 0.9
COS 0.1 0.1 0.1 0.1
Product steam d (saturated)
Gross, ex boiler, kg 755 929 990 755 793
Pressure, MPa 9 13 13 1.1 1.1
a
Aqueous emulsion of a highly viscous crude from the Orinoco basin in Venezuela.
b
1 m3 (STP) = 1 m3 at 0 ◦ C and 0.101325 MPa.
c
Expressed as 100 % oxygen; actual O2 -purity: 99.5 mol %.
d
Total steam from heat recovery boilers (basis: boiler feed water at 105 ◦ C); medium pressure boilers in quench mode are optional, product
gas may be fed directly to CO shift unit.

may also be suitable as feedstocks. Their use,
however, lies in the future.
Natural gas is still used as a feedstock for
the production of synthesis gases with a higher
ratio of carbon monoxide to hydrogen than is
achievable by steam reforming. For economical
reasons, partial oxidation of natural gas is used
in small plants and in regions where natural gas
is cheap. Lately it is considered as a means of
converting “stranded gas” into marketable liq-
uid products like methanol or synthetic fuel.
3.2. Partial Oxidation of Hydrocarbons
3.2.1. Principle
Partial oxidation is, in principle, the reaction of
hydrocarbons with an amount of oxygen insuf-
ficient for complete combustion at temperatures
between 1600 and 1350 ◦ C and pressures up to
15 MPa. It operates as a continuous process. The
basic reactions are as follows:
Cn Hm +n/2 O2
n CO+m/2 H2 (13)
Cn Hm +n H2 O
n CO+ (m/2+n) H2 (14)
Cn Hm +n O2
n CO2 +m/2 H2 (15)
The minimum amount of oxygen required for
complete conversion of the hydrocarbons is in-
dicated by Equation (13); 0.5 kmol of oxygen is
required for every kilomole of carbon. If the re-
action proceeds according to this equation, when
high-boiling distillates or residual oils (i.e., feed-
stocks with a large number of carbon atoms
per molecule) are being gasified sufficient heat
is generally produced to warm the reactants to
about 1500 ◦ C. Carbon monoxide and hydro-
gen are the main products until the hydrocar-
bons have been completely converted; only then
can carbon dioxide and water be formed from

surplus oxygen. Opinions differ on the reaction
sequence; some test results indicate that carbon
dioxide and water are primary reaction products
[40].
To prevent excessive temperature increase,
steam is usually added, which reacts endother-
mically with the hydrocarbons according to
Equation (14). This leads to the formation of
more hydrogen than would be expected from
conversion according to Equation (13).
The main elements of the hydrocarbon mix-
tures — carbon, hydrogen, oxygen, and sulfur
— are converted independent of the nature of
the feedstock, to the following thermodynami-
cally stable compounds: carbon monoxide, car-
bon dioxide, hydrogen, water, methane, hydro-
gen sulfide, and carbonyl sulfide. The propor-
tions of various components in the gas mixture
are determined by a range of equilibria, which
include the shift conversion:
CO+H2 O
CO2 +H2 (7)
the methane equilibrium:
CH4 +H2 O
CO+3 H2 (8a)
the hydrogen sulfide – carbonyl sulfide equi-
librium:
H2 S+CO2
H2 O+COS (16)
and
CO+1/2 O2
CO2 (2)
CH4 +CO2
2 CO+2 H2 (11a)
These equilibria are largely established in the
gasification reactor between 1500 and 1350 ◦ C.
They remain practically unchanged during very
rapid cooling by quenching with water or by in-
direct heat transfer to water boiling at a compar-
atively low temperature. Below 900 ◦ C, even an
approximation to equilibrium could be achieved
only by accepting very long residence times or
by using catalysts. The latter cannot yet be ap-
plied commercially because of soot formation.
The principal advantages of partial oxidation are
(1) the possibility of converting hydrocarbons
that cannot be vaporized and (2) the complete de-
struction of all carbon – carbon bonds; the only
hydrocarbon remaining in the raw gas is meth-
ane.
Gas Production 43
Methane formation is about ten times as high
as indicated by Equation (8 a); this is probably
due to the slowness of the reaction according to
Equation (11 a). As expected, increasing pres-
sure promotes methane formation; at 1400 ◦ C
and 3.0 MPa, the methane content of the prod-
uct gas is ca. 0.3 vol %, whereas it is 0.55 vol %
at 6.0 MPa. Methane content is also influenced
by changes in reaction temperature and addition
of larger or smaller amounts of steam.
Under conditions prevailing in the reaction
zone, no free carbon should be present, accord-
ing to either the Boudouard equilibrium
C+CO2
2 CO (10)
or the reaction
C+H2 O
H2 +CO (6)
Soot can be present in the raw gas only at be-
low 1200 ◦ C and around 5.0 MPa. Whereas the
amount of soot produced during partial oxida-
tion of methane is practically zero, in heavy-oil
gasification about 0.5 – 2.5 mass % of feedstock
is contained in the raw gas as free carbon. Some
authors assume that this soot formation is due
solely to thermal cracking of a proportion of the
hydrocarbons; others attribute it partially to the
Boudouard limit being reached during cooling.
Ash particles in the heavy oils also seem to act
as nuclei of condensation or catalysts for soot
formation [41, 42].
In heavy-oil gasification, soot formation can
be nearly eliminated by increasing the reaction
temperature, at the cost of a considerable in-
crease in oxygen consumption and a correspond-
ing increase in carbon dioxide content at the ex-
pense of carbon monoxide.
Sulfur components of the gas mixture are
largely hydrogenated according to Equation
(16). Under normal reaction conditions, ca. 95 %
of the sulfur is converted to hydrogen sulfide and
the remaining 5 % to carbonyl sulfide. No sulfur
di- or trioxide is detectable in the raw gas from
partial oxidation.
3.2.2. Types of Processes
Three processes are commercially established
for the production of gas mixtures (primary com-
ponents: H2 and CO) from gaseous or liquid hy-
drocarbons by partial oxidation: the Texaco, the
44 Gas Production
Shell, and the Lurgi process. The main steps of
all three processes are now practically identical.
The original differences between the pro-
cesses were that Texaco used natural gas as the
sole feedstock and changed to liquid hydrocar-
bons only after the process of steam reforming
of natural gas became available, whereas Shell
used heavy oils from the beginning. Lurgi’s pro-
cess in contrast was developed for lignite tar oils
and slurries and covers now the broadest range
of feedstocks.
What still distinguishes the processes today
are the methods of heat recovery and soot man-
agement. While all three use boiler configura-
tions for high-grade heat recovery, only Texaco
and Lurgi have available quench configurations
for heavy-duty services. On the other hand, all
three can offer some kind of soot recirculation
system while only Lurgi and Shell have built
more economic once-through systems, which
are also environmentally favorable.
Over 320 plants operating on these three pro-
cesses have been built to date.
Texaco Process. Originally, the Texaco pro-
cess did not have a waste-heat recovery boiler
(Fig. 15). Feedstocks are preheated as in the
other two processes. Fired heaters are often pre-
ferred to steam-heated ones for heavy oil as well,
probably by analogy with natural gas cracking
practice. Besides partial oxidation of natural gas
and residue oil, this process has been developed
further for partial oxidation of coal slurries (for
details, see Chap. 4).
Process steam is used to atomize the heavy
oil in the reactor, so the oil must be pressurized
to only a few bars above reactor pressure.
Oxygen is supplied to the reactor through
a central tube; the oil – steam mixture is fed
coaxially through an annular gap. The gas mix-
ture leaving the reaction zone is cooled to 250 –
300 ◦ C by quenching with hot water in a quench-
ing section of the reactor. Most of the soot
and ash is removed from the gas at the same
time, whereas the water vapor content increases
considerably due to evaporation of part of the
quench water. The water vapor content of the gas
is sufficient for conversion of the carbon monox-
ide to a residual content of ca. 1.8 – 2.5 vol % in
a downstream high-temperature conversion unit.
After leaving the quenching tank, the gas is
scrubbed again in a special venturi tube and a
soot scrubber (a packed column), which remove
the soot to a residual content of 1 – 2 mg/m3 . If
the gas is to be fed to a high-temperature con-
version unit, the soot is scrubbed out with hot
water.
Shell Process. The basic flow sheet of this
process resembles the one presented in Figure
16. The processes differ in the burner technol-
ogy, the soot removal and the soot/ash manage-
ment. The Shell process was right from the be-
ginning equipped with a waste-heat boiler and
is still available in this configuration only.
By means of reciprocating or centrifugal
pumps the heavy oil feedstock (as single stream)
is fed through a preheater to the reactor. The
so-called co-annular burner is of the steam-
atomizing type: oil, steam – oxygen mixture and
steam are routed through concentric, alternating
channels (slits) whose number determines the
capacity. Oil viscosities at the burner of up to 300
mm2 /s are manageable. The burner is cooled by
a pressurized circulating cooling water system.
The refractory-lined reactor and the waste-
heat recovery boiler are similar to those of the
other processes. Soot is removed from the raw
gas in two stages: most of it is washed out with
water in a quench tube [instead of the venturi
scrubber d) of Figure 15] and collected in a soot
separator. In the scrubber, a packed column, the
remaining soot is removed to a residual content
of < 1 mg/m3 . Preferably soot-free water from
the soot recovery unit is supplied to the top of the
scrubber, and soot-laden water from the scrub-
ber outlet is used for the quench tube. By cooling
the water fed to the scrubber, the gas is cooled
to slightly above ambient temperature. The soot
slurry is treated in a once-through soot/ash re-
covery and management system as described be-
low.
Lurgi Process. This process was originally
developed for the gasification of tars, oils, and
slurries formed as byproducts of fixed bed gasi-
fication. This lends to an inherent robustness (as
in slagging service) and flexibility (digesting un-
mixable feeds) which the refinery-derived pro-
cesses are lacking. The Lurgi process is available
in both, quench and boiler configurations.
Figure 16 shows the boiler configuration of
the Lurgi process with metals ash recovery sys-
tem. The feedstock is fed through preheaters
 Gas Production 45

Figure 15. Texaco gasification

a) Preheater; b) Reactor; c) Venturi scrubbing section; d) Soot scrubber; e) Decanter; f) Flash distillation; g) Naphtha column;
h) Water clarification

Figure 16. Lurgi oil gasification (boiler configuration) with metals ash recovery system (MARS)
a) Preheater; b) Reactor; c) Waste heat boiler; d) Venturi scrubber; e) Fine wash scrubber; f) Slurry tank; g) Filter; h) Multiple
hearth furnace; i) Return water vessel; j) Wastewater stripper

(a) to the reactor (b) by centrifugal pumps (or
reciprocating pumps for smaller capacities). A
pressure of only about 0.5 MPa above reactor
pressure is needed for operation of the steam-
atomizing burner. Preheating of feedstock and
oxygen is mainly done for optimization of the
process heat balance, i.e., to save on the costs
of heavy oil and oxygen otherwise consumed
for internal heating. The lowering of feedstock
viscosities is an additional — but welcome —
effect. The burner itself works well even with
viscosities up to 500 mm2 /s, meaning that ev-
ery pumpable feedstock can be gasified. This
top mounted multi-gun burner has the capabil-
ity of handling different, unmixable fluids, e.g.,
emulsions and slurries in addition to heavy oils.
The broken feed line represents such an optional
secondary feed.
The oxidant is preheated as well and mixed
with steam as moderator prior to being fed to the
46 Gas Production
burner. The burner and reactor are tuned by fluid-
dynamic simulation to achieve mixing of this
mixture with the feedstock within the smallest
possible volume. Thus, the reactor space is op-
timally used for gasification to completion. The
burner is water-cooled using a dedicated circu-
lating cooling water system at a pressure above
that prevailing in the reactor. The entire reactor is
refractory-lined. In the nonslagging service as-
sociated with boiler operation a refractory mate-
rial with high alumina content has achieved the
longest lifetimes.
The raw gas leaves the reactor at about
1350 ◦ C and passes directly into the heat re-
covery boiler (c) where 10 – 14 MPa steam is
formed while cooling the gas to a few degrees
above saturated steam temperature. This boiler
is specifically designed for the high gas inlet
temperatures and the particulates-charged gas
at high velocities. A small part of the steam
thus generated is used for feedstock and oxi-
dant preheating, the bulk is superheated for use
in steam turbine drives or in a combined cycle
power plant. The rest of the heat is recovered
in a boiler feed water economizer. Commonly,
most of the heat content of the gas below the
dew point is used to heat up make-up water or
turbine condensate in a water preheater after the
venturi scrubber.
The raw gas from the reactor contains a cer-
tain amount of free carbon (soot). The plant is
normally designed for a soot content in the gas
equivalent to 0.5 wt % of hydrocarbon reactor
feedstock. The soot in the gas is removed in a
two-stage water wash, which consists of a ven-
turi scrubber (d) and the fine wash scrubber (e).
The gas leaves the scrubber at 40 ◦ C at a resid-
ual soot content < 1 mg/m3 . The soot slurry,
which has an ash-soot content of 1 wt % car-
bon, is routed to the metals ash recovery system
(MARS, see below).
The Lurgi oil gasification is also available in
the quench configuration where the hot reaction
gas is brought down rapidly to saturation tem-
perature by direct water quench. This quench can
be selected for slagging service as in the original
application (coal – oil slurries, wastes) or for the
less severe high-ash, high-salt residue service. In
slagging service the reactor is lined with a spe-
cial high-chromium refractory which has proven
its resistance in many years of operation.
Like in the Shell process, the gas mixture pro-
duced contains approximately equal proportions
of carbon monoxide and hydrogen, ca. 5 % car-
bon dioxide, and small amounts of methane, ni-
trogen, argon, and hydrogen sulfide. Although
not equally well suited to all syntheses (mean-
ing those that require CO and H2 , as well as
those that require one of the two, either alone,
or either mixed with a third gas such as N2 ),
its composition is nevertheless neutral for many
uses. Methanol synthesis gas or hydrogen can
be produced by converting part or all of the car-
bon monoxide. If the necessary amount of nitro-
gen is added, ammonia synthesis gas can be pro-
duced. If the hydrogen – carbon monoxide ratio
remains unchanged, the gas is suitable, after pu-
rification, for oxo synthesis and for production
of maximum quantities of carbon monoxide by
low-temperature separation or absorption.
Soot/Ash Recovery and Management. In
the Texaco process, soot is extracted from the
soot water with naphtha in a closed system and
recovered for recirculation to the reactor. Shell
used an open system based on pelletizing in its
original process but was subsequently obliged to
change to a closed system also based on extrac-
tion with naphtha.
Due to difficulties with increased viscosities
of very heavy feedstocks, which makes carbon
recycle impossible, and due to poorer economics
of the recycle processes, once-through systems
were developed by Lurgi and Shell. These sys-
tems basically incinerate the soot after filtration
and recover the heavy metals as oxides.
Texaco Method (Fig. 15). Soot water is
mixed with naphtha, the soot and some of the
ash passing into the naphtha phase. After the two
phases are separated, practically soot-free water
from the decanter is depressurized in a flash
tank, to drive off dissolved naphtha. Naphtha is
recovered by condensation and recirculated to
the process; the same is true for naphtha-free
water.
The naphtha – soot mixture from the decanter
is mixed with heavy oil, and naphtha is distilled
off overhead in a distillation column. Oil collects
at the bottom of the distillation column together
with some ash and a residual amount of naphtha.
The oil is mixed with more heavy oil and fed to
the reactor via the oil heater.

Lurgi Metals Ash Recovery System (MARS,
Fig. 16). The problem of uneconomic carbon re-
cycle was solved by Lurgi through application of
its vanadium roasting technology. A proprietary
multiple hearth furnace is used for controlled
combustion of the soot under conditions where
the vanadium oxides neither melt nor corrode.
The soot slurry from the gasification (in both,
quench and boiler configurations) is flashed to
atmospheric pressure in a slurry tank (f). The
slurry is filtered (g) leaving a filter cake with
about 80 wt % residual moisture and a clear wa-
ter filtrate, which is partly recycled as quench or
scrubbing water. The filter cake is subjected to
a controlled incineration process in a multiple
hearth furnace (h). The product contains typi-
cally about 75 wt % vanadium pentoxide (plus
the nickel and iron from the crude), which can
be sold to metal reclaimers. The process is au-
tothermal, the heat of combustion being suffi-
cient to evaporate the moisture content of the
filter cake. Excess water is stripped of dissolved
gases in a wastewater stripper (j) and pumped to
final treatment.
Shell Method. Shell uses a similar system of
filtration and incineration. The main distinctions
to the Lurgi process as described above are in the
selection of key equipment like furnace and fil-
ters.
Selection Criteria for Quench Configura-
tion Versus Heat Recovery Configuration. In
addition to process-specific marketing strategies
there are technical and economic criteria for the
selection between quench and boiler configu-
rations (see Table 12). These must be studied
carefully for every application of the Texaco and
Lurgi processes that alone offer alternatives.
Generally speaking, the heat recovery config-
uration can be selected when the feedstock con-
tains low amounts of precipitation-prone con-
taminants, which could block the boiler tubes.
Most refinery heavy residues fall in this cate-
gory. In this case it is possible to run the gasifica-
tion at highest efficiency by generating consid-
erable amounts of high-pressure steam, which
also yields highest efficiency in a possible down-
stream integrated gasification combined cycle
(IGCC) power plant. The additional investment
in the boiler is recovered quickly.
Gas Production 47
Table 12. Comparison of quench and heat recovery configuration
Quench configuration Heat recovery
configuration
Feedstocks
Gas, residues, wastes, highest flexibility limited by possible
slurries (sludges, coal, salt precipitation
coke), extreme ash
and/or salt contents
Product range:
H2 + CO, H2 , CO fastest (cheapest) highest flexibility
route to H2 and NH3
Energy utilization:
Steam production MP * steam available HP ** steam, heat
trade off efficiency vs.recovery at highest
cost temperature, highest
efficiency for IGCC
possible
Investment cost: lowest cost for HP ** waste-heat
gasification unit boiler (high
efficiency) at extra
cost
* MP = medium pressure.
** HP = high pressure.
On the other hand, should the feedstock con-
tamination be above the waste heat boiler’s lim-
its, the quench configuration has to be chosen.
It also may be selected when such contaminated
feeds are expected in later operation of the re-
finery or, when the customer wants to keep open
all options for feedstocks like coke/coal slurries
and wastes. The quench configuration thus of-
fers highest (potential) flexibility at lowest in-
vestment cost traded off against a loss in energy
efficiency.
The product side also influences the selec-
tion, e.g., for hydrogen or ammonia as product
it is more economical to route the quenched, i.e.,
hot saturated gas directly into a raw gas shift con-
version unit (see Section 5.1) instead of cool-
ing it down and desulfurizing it before the shift.
This is because the water quench raises all the
steam necessary for the CO shift reaction di-
rectly within the reactor effluent. If a syngas rich
in CO is required, the heat recovery configura-
tion is the appropriate choice.
3.2.3. Influencing Raw Gas Composition
Different types of gas are produced not so much
by changing operating conditions (e.g., pres-
sure and temperature) as by changing the pro-
portions of reactants, adding carbon dioxide,
and employing further process steps immedi-
ately downstream of actual gasification. Com-
mercially produced gases can be classified in
48 Gas Production
three large groups: synthesis, fuel, and reduc-
tion gases.
An overview of gas yields and compositions
in relation to the feedstock and gasifying media,
together with other important data, is presented
in Table 13.
Synthesis Gas. Synthesis gas must nearly al-
ways be low in undesirable gas components such
as methane, nitrogen, and argon, and high in
either carbon monoxide or hydrogen, or both.
Medium to high pressure is desirable as well.
Whereas the nitrogen and argon contents of un-
purified synthesis gas depend almost exclusively
on the quality of air separation (nitrogen com-
ponents of heavy oils generally cause a rise of
less than 0.1 % in the nitrogen content of the
gas), the methane content is largely a function
of gasification pressure (see Section 3.2.1).
The proportions of gasification steam, oxy-
gen, and heavy oil are the same for almost all
synthesis gases, regardless of whether hydro-
gen- or carbon monoxide-rich gases or gases
with a defined ratio of hydrogen to carbon
monoxide are produced. For the last category,
which includes primarily synthesis gases for the
production of oxo alcohols, carbon dioxide must
be recycled to the reaction zone to increase the
carbon monoxide content of the synthesis gas
and obtain the correct ratio of hydrogen to car-
bon monoxide (which can range from 1: 1 to 1:
1.5 for certain oxo processes).
To manufacture synthesis gases in which no
(or only partial) conversion of carbon monox-
ide to hydrogen and carbon dioxide with steam
occurs, use of the waste-heat boiler to cool the
hot reformed gas is preferred to quenching with
water or steam. Examples are gases for carbon
monoxide production, some oxo processes, and
methanol synthesis.
A special case is partial conversion of car-
bon monoxide immediately following the gasi-
fication reaction. This can be brought about by
quenching with defined quantities of water or
steam, either in the bottom section of the gasi-
fication reactor or in a quench tube located bet-
ween the reactor and the waste-heat boiler.
Here, best results are achieved by using steam
and cooling the gas to ca. 1000 ◦ C. At lower tem-
perature, the water gas equilibrium, (Eq. 7) can-
not be reached without a catalyst. A very flexi-
ble and economic alternative is the use of a direct
quench reactor in parallel to a reactor/waste-heat
boiler train.
If, on the other hand, production of hydrogen-
rich synthesis gas is desired, direct quenching
of the hot synthesis gas, followed by catalyst-
based shift conversion is the preferred route.
An example is the production of ammonia from
heavy oil in countries with cheap coal reserves
and little oil of their own, (e.g., India), which
are able to supply coal-based energy at low cost
(whether directly from steam or indirectly via
electric power).
Oxygen with a purity of > 95 % is used for
gasification. In fact, the oxygen content is usu-
ally > 99 %, because the cost of achieving the
higher purity is always less than the extra cost
of gas purification and synthesis (e.g., by ad-
ditional consumption of synthesis gas) to com-
pensate for hydrogen or carbon monoxide losses
from increased discharge of purge gas.
The possibility of manufacturing ammonia
synthesis gas from heavy oil by gasification with
enriched air (i.e., with a N2 – O2 mixture con-
taining > 21 % O2 ) has also been proposed but
not exploited commercially. The higher costs of
purifying and conditioning the gas that result
from the increased volume of synthesis gas be-
cause of its nitrogen content outweigh the sav-
ings in gasifying medium. (Enriched air can be
produced from air by mixing with pure oxygen
or by adsorptive depletion of nitrogen.)
Fuel Gas. In contrast to synthesis gas pro-
duction, a low content of inerts is not particularly
important for the manufacture of fuel gas. Only
the required heating value determines the gasi-
fying medium, pure oxygen or air. Combustion
of larger volumes of gas instead of gas with an
increased heating value is often justifiable eco-
nomically. However, not only the heating value
but also the density and thus the Wobbe index
(see Section 8.2.1.3) of the fuel gas are almost
always stipulated for reasons of interchangeabil-
ity with fuel gases from different sources. When
fuel gases containing carbon monoxide are used
in the private sector, it is mandatory to minimize
their toxicity by limiting the carbon monoxide
content, generally to between 1 and 3 vol %.
Hot Carburetion. Fuel gas specifications
for the private sector require heating values rang-
ing from 17 500 (town gas) to 34 000 kJ/m3
 Gas Production 49
Table 13. Typical results of partial oxidation (basis: Shell gasification)
Type of gas: Untreated raw gas Synthesis gas, Fuel gas, Fuel gas, Reduction
(H2 -rich) carbureted low-calorific gas
Feedstock: Bunker-C fuelVacuum Bunker-C fuel (with soot recirculation)
(without soot residue (with
recirculation) soot
recirculation)
Operating pressure, MPa 6 6 6 6 1.5 35
Preheating temperature, ◦ C
Heavy oil – natural gas 245 280 245 245 245 245
O2 – air 245 260 245 245 400 245
Steam 310 360 310 310 310 310
CO2 245
Feedwater 160 105 160 160 160 160
Feed quantities
Feedstock, pure kg 100 100 100 100 100 100
O2 (98 – 99.5 %), m3 77.6 70.7 74.1 73.7 81.2
Air, m3 450
Steam, kg 45 50 45 45 30
Quenching steam – water, kg 100 * 60 **
CO2 , m3 50
Light naphtha, kg 65
Product gas volume, m3 303 290 327 354 602 305
Gas composition, vol %
CO2 4.32 4.63 13.34 13.32 2.36 7.68
CO 46.55 48.92 33.29 31.02 22.34 52.29
H2 47.15 44.94 51.49 26.68 16.71 38.03
CH4 0.60 0.3 0.60 27.79 0.03 0.60
N2 + Ar 0.56 0.2 0.54 0.49 57.70 0.60
H2 S + COS 0.81 1.01 0.73 0.70 0.16 0.80
Lower heating value (LHV), kJ/m3 11 365 10 105 16 897 4670 11 077
Steam output, kg 275 258 301 252 580 320
Steam pressure, MPa 10.5 8 10.5 10.5 10.5 10.5
Steam exported, kg 230 213 118 207 540 290
* Steam.
** Liquid.

(natural gas). However, gasification of heavy oil
produces heating values of only 4000 – 11 000
kJ/m3 , depending on whether air or oxygen is
used as the gasifying medium. Thus, the heating
value must be improved. This can be achieved
— after appropriate gas conditioning — either
by methanation without addition of other fu-
els or by hot carburetion with addition of liquid
hydrocarbons having a low final boiling point.
Methanation is necessary if heating values > 20
000 kJ/m3 are required. For the production of
town gas with heating values between 16 500
and 19 000 kJ/m3 , however, hot carburetion is
more beneficial from the heat economy aspect,
because it operates with practically no addi-
tion or subtraction of heat. This is in contrast
to the strongly exothermic methanation process,
in which about 10 500 kJ (i.e., ca. one-fifth the
heating value of the feedstock) must be dissi-
pated per cubic meter of methane formed.
Due to the widespread availability of natu-
ral gas — in some places as LNG — carburetion
has lost most of its significance as a commercial
process.
As can be calculated with the aid of Table
13, the thermal efficiency (i.e., ratio of the heat-
ing value of the product gas to the heating value
of the fuel) is 81 % for normal gasification and
increases to 89 % with hot carburetion, at the ex-
pense of reduced generation of steam from waste
heat.
Fuel Gas for IGCC Power Plants. A special
area of fuel gas production is for gas turbines in
power plants. Due to increasingly stringent air
pollution control regulations, operating coal- or
oil-fired steam boilers without flue gas desulfu-
rization systems is impossible. Because clean-
ing large gas volumes at slightly above atmo-
spheric pressure is very expensive, attempts have
been made to find a more economic solution by
50 Gas Production
applying fuel gasification with subsequent gas
cleaning under pressure. As shown in Figure 17,
partial oxidation of heavy oil can be combined
beneficially with a gas turbine-driven generator,
not only from the point of view of gas cleaning
but also with regard to generation of high-pres-
sure steam. For the arrangement illustrated, an
efficiency well above 46 % is achieved, 2 – 4 %
better than for a conventional steam boiler power
plant [43].
IGCC Power Plants (Fig. 17). A heavy refin-
ery residue is gasified with oxygen from an air
separation unit (i) in a Lurgi oil gasification
plant (a) at 6.5 MPa, producing a lean gas with
a heating value of 11 000 kJ/m3 . Oxygen and
residue are preheated to 280 ◦ C. Cooling in the
waste-heat recovery boiler produces high-pres-
sure steam at 13.0 MPa. After the soot is re-
moved as described above and the gas is cooled,
carbonyl and hydrogen sulfides and all other
trace contaminants are removed to 20 ppm in
one step in a Lurgi Rectisol unit (b) (see Section
5.4.2.1). The desulfurized gas passes through a
gas expander (f) generating electric power and
refrigeration to cool the methanol within Recti-
sol. This dual use expansion adds significantly
to the overall efficiency of power generation.
The low-calorific gas is burned in a gas tur-
bine (d). For NOx -control the gas is further di-
luted by saturation with water and — optionally
— with nitrogen from the air separation unit.
Waste heat from the gas turbine off-gas and the
saturated steam from the gasification are used
in the waste-heat steam generator (h) to produce
additional steam and to superheat steam. The en-
ergy of the superheated steam is used in a con-
densing steam turbine (g) that drives a generator
(e). For maximum efficiency the steam system
will be designed for three levels with one or two
reheat stages.
The gas turbine is also coupled to an air com-
pressor in which combustion air for the gas tur-
bine is compressed. A part of this compressed
hot air can be routed through a cooler – saturator
system producing steam for fuel gas saturation
before entering a medium pressure air separation
saving the separate air compressor. The nitrogen
from the air separation in turn can be recycled
back to the gas turbine for NOx -control and to
maintain the mass flow of the turbine. Air and ni-
trogen integration as described yields higher ef-
ficiency than a nonintegrated system with inde-
pendent air separation unit (ASU) compressor,
but involves increased complexity of the plant.
Therefore different designs with varying degrees
of integration exist to accommodate for all re-
quirements. Many versions of this IGCC process
exist, some of which export steam or synthesis
gas together with electrical power. Coproduction
of this type results in better overall economics
for a plant.
A good example for this concept is a refer-
ence plant for the Lurgi oil gasification (SVZ,
Schwarze Pumpe, Germany) where the oil gasi-
fier together with coal-waste gasifiers produces
a synthesis gas which is fed to a combined cy-
cle and a methanol plant [44]. Another example
is a large refinery in Pernis (The Netherlands)
where a Shell gasification feeds two thirds of its
capacity to a hydrogen production plant and one
third to an IGCC power plant [45].
Reducing Gas. Gas produced from heavy oil
is also used in ore reduction. The carbon diox-
ide and water vapor content or reducing gases
must be as low as possible. Water vapor can
be removed easily from the gas by condensa-
tion, which presents no problem if the gas has
been freed of soot, sulfur, and carbon dioxide.
However, for reduction of less sensitive ores,
uncooled or only partly cooled, soot-laden gas
manufactured from low-sulfur oils is used when-
ever possible. Thus, water vapor content may be
an important element of the gas composition.
The quality of reducing gases is measured by
the degree of oxidation η, which is defined as
follows:


cH2 O +cCO2 ·100
η0 = (%)
cH2 O +cCO2 +cH2 +cCO
Degrees of oxidation ≤ 5 % are the goal (see
Table 13).
Reducing gases, which are always produced
directly alongside the ore reduction furnace, dif-
fer from synthesis and fuel gases in pressure and
temperature. Synthesis and fuel gases must be
maintained at high pressure and below ambient
temperature: for synthesis gases, with regard to
gas purification and compression; for fuel gases,
with regard to gas purification, distribution, and
storage. For admitting reducing gas to the shaft
furnace, a slight overpressure is sufficient; on
the other hand, a temperature up to 1000 ◦ C is
desirable. The pressure range for manufacture
 Gas Production 51

Figure 17. Lurgi oil gasification for combined cycle power plants
a) Oil gasification; b) Gas purification; c) Sulfur recovery; d) Gas turbine; e) Generator; f) Gas expander; g) Steam turbine;
h) Heat recovery steam generator; i) Air separation; j) Air compressor (compressed air for air separation may be extracted
from air compressor for gas turbine); k) Nitrogen compressor (optional); l) Motor; m) Combustion chamber

Carbon dioxide 7–9 Ethylene 6–7

of reducing gas is currently 0.3 – 0.5 MPa, but Carbon monoxide 40 – 45 Propylene 1–2
efforts are in progress to achieve ore reduction Hydrogen 23 – 30 Higher olefins and 0–5
at ca. 2 MPa. acetylenes
Methane 4–5

From the residual gas, 3.5 t of ammonia, for in-

3.2.4. Submerged Flame Process
The BASF submerged flame process is also a
partial oxidation process; it was developed to
produce acetylene (→ Acetylene, Chap. 4.2.3)
and ethylene from natural gas and crude oil.
Its distinctive feature is maintenance of a flame
beneath the surface of the oil sump, to ensure
high temperature and short residence time. Hot
gases produced by partial combustion and crack-
ing, which have a temperature of ca. 1500 ◦ C,
are quenched almost instantly to 250 ◦ C in the
hot oil sump. Thus, the thermodynamic equilib-
rium for the high temperature is “frozen”. As in
other partial oxidation processes, soot is formed,
which collects in the oil sump and is recirculated
to the burner. After condensable cracking prod-
ucts are removed, the cracked gas, which still
contains a small amount of soot, is scrubbed with
condensate. The condensate is then recirculated
to the submerged burner.
The process operates between 0.2 and 1.0
MPa and yields a cracked gas with the following
approximate composition, in percent by volume,
which can be processed into synthesis gas:
stance, can be produced per tonne of acetylene.
3.3. Hydrogenating Gasification
Hydrogenating gasification, like partial oxida-
tion, is a continuous process.
Principles. In contrast to partial oxidation,
hydrogenating gasification is not based on com-
bustion of part of the feedstock; instead, a hy-
drogenation reaction which proceeds exothermi-
cally overall takes place with addition of hydro-
gen. Liquid hydrocarbons are cracked primar-
ily to form methane and ethane. This process,
therefore, is beneficial for the production of fuel
gases with a high heating value: on the other
hand, direct manufacture of carbon monoxide-
and hydrogen-rich synthesis gas is not possible
[46].
Gas Recycle Hydrogenator (GRH) Pro-
cess. The British Gas Corp. began to develop
the GRH process in the early 1960s [47]. This
enables the conversion of liquid hydrocarbons
with a final boiling point up to ca. 325 ◦ C to
a gas mixture consisting mainly of hydrogen,
methane, and ethane under controlled tempera-
ture and pressure in a shaft reactor, termed the
52 Gas Production
hydrogenator. Hydrogenating gasification pro-
duces no soot. The reaction takes place at 1.8
– 7.0 MPa and 350 – 500 ◦ C at the inlet or ca.
750 ◦ C at the outlet, depending on the boiling
range of the feedstock. The latter must contain a
certain amount of sulfur (about 10 ppm), which
acts as a poison on reactor components made of
nickel alloy, to prevent them from acting as cat-
alysts that might lead to soot formation from the
hydrocarbons. After desulfurization, aromatics
removal and methanation, an SNG may be pro-
duced with a higher heating value (HHV) of 39
100 kJ/m3 , and a pressure of 6.0 MPa. The ther-
mal efficiency of the process is 85 %.
Fluidized-Bed Hydrogenation (FBH) Pro-
cess. The FBH process, also developed by the
British Gas Corp., enables gasification of crude
and extremely heavy oils. Feed oil and hydrogen
are superheated and fed into the FBH reactor, in
which hydrogenation of the hydrocarbons takes
place in a fluidized bed formed from coke bet-
ween 700 and 820 ◦ C. The most important pro-
cess variables are temperature, residence time,
and oil: hydrogen ratio. Part of the hydrogen is
supplied to the reactor through a grate from be-
low to fluidize the coke.
Most of the hydrogen is mixed with the oil
and sprayed from below into a central tube. By
this means, rapid circulation is achieved in the
reactor. The oil evaporates at the outlet of the
spray nozzle. Any oil that does not evaporate ad-
heres immediately to the flowing coke particles
and is entrained with them. If the raw material
contains residue-forming components, coke par-
ticles are also formed. Therefore, a small amount
of coke must continually be withdrawn from the
reactor.
Gas leaving the reactor is quenched with light
aromatics, and the condensate is removed from
the rich gas. Most of the sulfur in the oil is con-
verted to hydrogen sulfide. A gas produced from
Algerian crude with the addition of ca. 6.5 kg of
hydrogen per kilogram of oil has a HHV of 39
400 kJ/m3 at a pressure of 5.0 MPa. For SNG
production, gas from the FBH plant must un-
dergo a second hydrogenation step to reduce its
hydrogen content [48]. More details on both pro-
cesses, GRH and FBH, may be found in [49].
4. Gas Production from Coal, Wood,
and Other Solid Feedstocks
This chapter deals with the production of gases
from solid carbonaceous materials such as coal,
peat, wood, solid wastes and solid residues
from petroleum upgrading (delayed coke, etc.).
The gasification process occurs via pyrolysis
reactions (thermal decomposition) and subse-
quent heterogeneous (gas – solid) reactions of
the solid residue from pyrolysis with reactive
gases (O2 , steam, CO2 , H2 ).
Besides carbon, solid feedstocks contain
other elements such as hydrogen, oxygen, nitro-
gen, sulfur, heavy metals, and trace elements in
varying amounts. The feedstocks are converted
to a gaseous product suitable for use either as a
source of energy or as a raw material for the syn-
thesis of chemicals and liquid or gaseous fuels.
The gaseous product can be handled with maxi-
mum convenience and purified easily from com-
pounds that would cause pollution problems.
Thus, gasification is an upgrading process that
greatly extends the uses of solid fuels.
During their long history, the science and
technology of solid feedstock gasification have
advanced in various stages induced by external
factors. At first directed toward the production
of fuel or town gas for lighting and heating, the
interest in gasification shifted in the first half of
this century to synthesis gas for the production
of chemicals and liquid motor fuels.
After a period of increasingly intense com-
petition from oil and natural gas, gas produc-
tion from solid feedstocks has become less im-
portant since the 1940s. In the late 1960s and
early 1970s, some industrialized countries began
to expect natural gas shortages which, together
with oil price increases, changed the attitude to-
ward utilization of solid fuels, particularly coal
available in many parts of the world. More and
more, the finite nature of fossil fuel reserves, the
need for conservation, and good resource man-
agement became accepted and the significance
of the world’s coal reserves was recognized. In-
terest in coal utilization increased, primarily in
the fields of gasification and liquefaction (→
Coal Liquefaction), and large sums of money
became available from governments for the re-
search, development, and demonstration of new
processes and the improvement of existing ones.
More recently, since large resources of natural

gas have become available, the interest in coal
gasification has decreased considerably.
Petroleum-derived residues have gained
some attention as feedstocks for gasification,
with the increasing yield of residues in petro-
leum refining because of decreasing oil quality
and the need for their economic and environ-
mentally acceptable utilization, for example, for
H2 production. Use of wood as a feedstock has
played a continuous role in small-scale gasifi-
cation units (e.g., for the production of gaseous
fuels) and more recently gained interest in the
context of biomass energy applications.
Advances in gasification have been made
possible by progress in other fields. Fundamen-
tal research on the mechanism and kinetics of
chemical reactions, mass and heat transfer, fluid
dynamics, and mathematical modeling has con-
tributed to a better understanding of the phenom-
ena occurring in gasification processes long after
their successful operation started.
This chapter introduces fundamental aspects
and process technologies of gas production from
solid feedstocks. Given the variety of new de-
velopments in the past decades, only a selection
can be presented here to help identify and dis-
cuss basic principles, state of the art, and future
trends. For more details, the reader is referred
to review articles on gasification fundamentals
[50 – 52], gasification processes [53 – 59], or
both [60, 61], and to numerous publications on
this subject.
4.1. Fundamentals
Gasification of solid feedstocks involves the
complex interaction of chemical reactions and
physical processes such as heat and mass trans-
fer.
Figure 18 shows a scheme of the main chem-
ical reactions that occur when carbonaceous ma-
terials are exposed to reactive gases at high tem-
perature. The yield and composition of the prod-
uct are determined by the combined effects of
feedstock properties and reaction conditions on
the thermodynamics and kinetics of individual
reactions. For example, the yields of liquid by-
products (e.g., tar, phenols) depend on the re-
action conditions that prevail during pyrolysis
and secondary reactions of the volatile products
(e.g., temperature, gas-phase residence time).
Gas Production 53
4.1.1. Thermodynamics of Chemical
Reactions
Some reactions of the scheme in Figure 18 are
endothermic, in particular the gasification re-
actions of char with steam or carbon dioxide,
which are significant in most gasification pro-
cesses. (For heat effects of individual reactions,
see Chap. 1)
The resulting heat requirement is met either
by reactions with oxygen (in autothermic pro-
cesses) or by an external heat source (allothermic
process). Minimization of overall heat require-
ments has been one incentive among others for
improving process efficiencies and economics.
For example, the idea of applying reaction
conditions that favor the overall reaction
2 C+2 H2 O → CH4 +CO2
which is nearly thermoneutral, has affected
gasification process development efforts during
the times when production of CH4 from coal
appeared attractive.
In some of the chemical reactions of Fig-
ure 18, conversion is limited by equilibrium
constraints under typical gasification conditions
(temperature, pressure). Most significant in this
respect are the reactions of char with steam, car-
bon dioxide, and hydrogen. Equilibrium con-
stants for these and other reactions, as well as the
effect of temperature, are presented in Chapter
1.
Thermodynamic analysis may aid in exam-
ining the limits for conversion and product gas
composition as affected by such process vari-
ables as temperature, pressure, and stoichiome-
try. For example, the effect of temperature and
pressure on equilibrium gas composition for in-
dividual char – gas reactions with steam, carbon
dioxide and hydrogen is shown in Figure 19. The
curves reflect two general equilibrium princi-
ples: (1) higher temperature favors products of
endothermic reactions and (2) higher pressure
shifts the equilibrium in the direction of lower
amounts of gaseous components. Some past in-
centives of process development were based on
thermodynamic analyses of gasification. For ex-
ample, to produce methane-rich gases (substi-
tute natural gas, SNG), high pressure and low
temperature are advantageous under equilibrium
54 Gas Production
Figure 18. Main chemical reactions during gasification of solid carbonaceous materials
aspects. As a consequence, research and devel-
opment efforts were directed toward applying
higher pressure and enhancing feedstock reac-
tivity (e.g., via catalysis), thereby lowering gasi-
fication temperature.
Figure 19. Effect of temperature and pressure on equilib-
rium gas composition in the presence of solid carbon
However, only the limits of conversion and
product gas composition can be identified by
thermodynamic analysis. In real gasification
systems, equilibrium is generally not reached
because of kinetic constraints.
4.1.2. Kinetics
Pyrolysis Reactions. Among the chemical
reactions that occur during gasification, pyro-
lysis is generally fast. This is illustrated in Fig-
ure 20, which presents first-order rate constants
of some reactions shown in Figure 18. Underly-
ing values for activation energies and preexpo-
nential factors are taken from various literature
sources (Table 14). Formation of tar, methane,
and hydrogen as volatile products from Mon-
tana lignite is presented as part of pyrolysis.
The rates of primary pyrolysis product for-
mation can be described by
dVi
= k0i exp (−EAi /RT ) (Vi∗ −Vi ) (14)
dt
where V i is the total amount of product evolved
from reaction i until time t, and V i * is the value
of V i at t → ∞.
Kinetic parameters for pyrolysis product for-
mation have been determined for various kinds
of coal and experimental conditions. Extensive
compilations of pyrolysis data and kinetic infor-
mation drawn from them can be found in review
papers [51, 62].
Char – Gas Reactions. Of the char – gas re-
actions, combustion is generally fastest, and
gasification is generally faster with steam than
with carbon dioxide and hydrogen.
 Gas Production 55
Table 14. Examples of first-order rate constants for reactions occurring during gasification (for nomenclature, see text)
k0 , EA , V *, Reference
s−1 J/mol wt %, (maf) b
Pyrolysis product formation tar 2.0×1017 315 281 3.5 (+ 2.9) [63] (lignite)
CH4 4.7×1014 290 578 1.1 (+ 0.4) [63] (lignite)
H2 1.6×1018 371 806 0.6 [63] (lignite)
Char – gas reactions C – O2 1.8×106a 113 050 [64] (bituminous coal)
C – H2 O 4.1×102a 146 545 [65] (subbituminous coal), [66]
C – CO2 2.5×102a 146 545 [65] (subbituminous coal), [66]
C – H2 8.4×10−4a 67 201 [65] (subbituminous coal), [66]
Tar cracking coal tar 1.2×109 164 968 [67] (bituminous coal)
8.0×1012 272 992 [67] (bituminous coal)
a
For (pi – pei q ) = 1.013×105 Pa (see Eq. 15).
b
maf = moisture and ash free.

where pi is the partial pressure and peq

i the equi-
librium partial pressure of reactant i, and mc is
the mass of solid carbon in the char. Values of
k 0 and E A for char – gas reactions vary with the
kind of solid feedstock, according to its reac-
tivity. Values of gasification rate constants for
chars derived from various feedstocks vary with
up to eight orders of magnitude. High transient
reactivities can be observed under rapid heating
conditions, (i.e., when pyrolysis and gasification
of the resulting char occur simultaneously). Ki-
netic parameter values for char – gas reactions
in Table 14 are taken from a modeling study of
coal gasification in moving-bed reactors.
A characteristic of gas – solid reactions is the
existence of a regime of temperature and pres-
sure in which mass transfer affects overall ki-
netics. Extra- and intraparticle mass-transfer re-
sistance can be incorporated in Equation (15) as
follows:
d mc

= −keff mc pi −peq
i (16)
dt
1
keff = 1
(17)
kg
+ η 1k
r

where k g is an extraparticle (film) mass-trans-

Figure 20. Examples of first order rate constants for re-
actions during gasification (pyrolysis product formation: fer coefficient; k r , a first-order chemical reac-
Montana lignite [63], tar cracking: bituminous coal [67], tion rate constant; and η, an effectiveness factor
char – gas reactions: bituminous and subbituminous coal that includes resistance to pore diffusion. The
[66] theoretical background can be found in reaction
Pyrolysis product formation: a) Tar; b) H2 ; c) CH4 ;Char –
gas reaction: e) C−O2 ; f) C−H2 O; g) C−CO2 ; h) C−H2
engineering textbooks (e.g., [68]; → Fluidized-
Bed Reactors).
The temperature dependence of Equation
Although detailed kinetics include noninte-
(17) in its general form is shown in Figure
ger reaction orders and inhibiting effects of re-
21. Accordingly, the chemical reaction is rate-
action products, simple first-order rate laws can
controlling at lower temperature because it has
be used for estimating and modeling purposes:
dmc

the highest activation energy and extraparti-
= −k0 exp (−EA /RT ) mc pi −peq
i (15) cle diffusion is limiting at high temperature.
dt
56 Gas Production

In between ranks the intraparticle mass-trans-
fer regime. Because these regimes may all play
a significant role in technical gasification their
limits must be defined by means of kinetic reac-
tor analysis. The effects of feedstock reactivity,
particle size, gas flow rate, and total pressure are
discussed in [52].
where ci is the molar (or mass) concentration of
species i in the gas phase.
Values of kinetic parameters for tar cracking
given in Table 14 were determined with freshly
formed tar from bituminous coal [67].
Equations (14) – (16) and (18) can be used
for describing source or sink terms in the bal-
ance equations in reactor models (see Section
4.2.3).

4.2. Classification and General

Characteristics of Gasification Processes

4.2.1. Criteria for Classification

Processes for gasification of solid carbonaceous

materials may be classified in the following ways
(the abbreviations given are used in subsequent
tables that present information on individual
gasification processes):
1) Method of contacting solid and gaseous reac-
tants (type of gasification reactor)
moving fixed bed
fluidized bed
entrained flow
molten bath
2) Kind of solid feedstock
coal
Figure 21. Temperature dependence of effective rate con-
stant for gas – solid reactions with porous particles, sche-
wood – biomass
matic representation solid waste materials
A) Film-diffusion controlling (cG gas concentration, δ film petroleum-derived residues
thickness) 3) Particle size of solid feedstock
B) Pore diffusion controlling
C) Chemical reaction rate controlling
fine
medium
coarse
Gas-Phase Reactions of Volatiles. Gas- 4) Gasifying medium
phase reactions of volatile pyrolysis products in- air (air)
clude a variety of individual reactions. Among oxygen (ox)
them are cracking, reforming, combustion of steam (st)
tarry species and hydrocarbons, dealkylation, steam – air (st/a)
dehydroxylation, and shift conversion of carbon steam – oxygen (st/ox)
monoxide. hydrogen (hydr)
The rates of these reactions depend, in a com- 5) Method of supplying heat required by gasifi-
plex way, on the reactivity of the reacting species cation reactions
and on reaction conditions (partial pressures, internal heating
temperature, catalytic effects). autothermic (I/A)
Again, first-order laws are sufficient for esti- cyclic (I/C)
mating and modeling purposes: heat-carrying fluids or solids (I/HC)
d ci external heating (E)
= −k0 exp (−EA /RT ) ci (18)
dt

heat transferred through walls of reaction
vessel or heat exchanger (allothermic)
6) Operating pressure
atmospheric
elevated
7) Condition of gasification residue to be re-
moved
dry ash in nonslagging operation
slag in slagging operation
8) Application of product gas
fuel gas (medium or low Btu) (FG)
fuel gas for combined cycle power plant
(FG/ IGCC)
synthesis gas (SG)
substitute natural gas (SNG)
source of hydrogen (H2 )
gas for direct reduction of iron (RG)
9) Developmental status
commercially available process
process in developmental stage
bench scale
pilot-plant scale
demonstration scale
Obviously, these criteria are not independent,
and others could be used instead. An exam-
ple is a characteristic gasification temperature,
which determines product gas yield and compo-
sition, utility consumption, and the approach for
predicting product gas composition and process
performance (see Section 4.2.3).
For the purpose of this chapter, processes are
presented according to the method of bringing
the reactants into contact. This appears to be
the most appropriate way of identifying process
principles and characteristics, and is the most
widely applied and accepted practice. Figure 22
shows examples of reactor types that represent
different methods of contacting reactants.
4.2.2. Criteria for Process Assessment
Besides economics and availability, efficiency
and other process performance criteria charac-
terize individual gasification processes and aid
in their comparison and assessment. Some com-
monly used criteria for practical purposes are
defined in the following material.
Gas Production 57
Efficiencies
(Lower heating values are often used instead
of higher heating values.)
Carbonconversion =
1− carboningasificationresidue
carboninsolidfeedstock
Specific Gasification Rates
– Gas production rate per unit volume of gasi-
fier
– Gas production rate per unit cross section of
gasifier
Specific Production and Consumption Fig-
ures
– Gas (or byproduct) production per unit mass
of solid feedstock
– Utility consumption per unit mass of solid
feedstock
– Utility consumption per unit volume of prod-
uct gas
4.2.3. Mathematical Modeling of
Gasification Reactors
Mathematical models have gained importance as
practical tools for designing gasification reactors
and improving their operation and control. The
general aim is to predict and interpret gasifier
performance features such as
Product gas yield and composition
Utility consumption figures
Efficiency
Response time to input changes
as affected by
1) Solid feedstock characteristics (e.g., proxi-
mate and ultimate analysis, reactivity), and
2) Design and operational parameters (e.g., gasi-
fier size, pressure, composition of gasifying
medium).
58 Gas Production

Figure 22. Types of gasification reactor representing different methods of contacting reactants and operating temperatures
A) Moving bed (nonslagging, countercurrent); B) Fluidized bed; C) Entrained flow; D) Molten bath

The degree of detail and the complexity of
mathematical models depend on the particular
type of gasifier and the task to be addressed.
Progress in computing and in efficient algo-
rithms, as well as the interest in coal gasification,
led to numerous modeling activities and higher
sophistication of models during the 1970s and
later.
For gasification reactors, the following types
of models are most widely applied:
1) Blackbox models (empirical correlations),
2) Equilibrium models, and
3) Kinetic models.
Blackbox Models (Empirical Correla-
tions). Experimental data form the basis for
correlation of commercial-size gasifier perfor-
mance with feedstock characteristics and opera-
tional parameters. Such correlations are of great
practical importance for all types of gasification
processes. They usually require little fundamen-
tal knowledge and mathematical effort. How-
ever, because they are not based on fundamental
principles, their usefulness for inter- or extrapo-
lation is limited.
Equilibrium Models. Equilibrium models
are valuable for identifying limits of conversion
and product yields and for predicting reactor out-
let conditions. This description is approximate
because chemical equilibrium is usually reached
only after long reaction times. Reaction rates
become slow when equilibrium is approached,
leading to long residence times or large reactor
volumes to attain equilibrium conversion. How
well an equilibrium approach can describe re-
actor outlet conditions in a real system depends
on the rates of chemical reactions, mass transfer,
and convective flow of reactants.
Equilibrium models are well established
for high-temperature gasification systems
(entrained-flow and molten-bath reactors),
where chemical reactions are sufficiently rapid
to approach thermodynamic equilibrium (e.g.,
[69]).
In gasifiers where product gas composition
results from reactions occurring at lower tem-
perature (e.g., fluidized-bed or moving-bed re-
actors), a defined deviation from chemical equi-
librium can be incorporated by means of cor-
rective factors for equilibrium constants or tem-
Gas Production 59
perature differences between actual and equilib-
rium values [70, 71]. However, these restricted
equilibrium parameters generally cannot be cor-
related with feedstock properties and operating
variables on a fundamental basis. Therefore, ca-
pabilities for extrapolation are limited.
Kinetic Models. Kinetic models offer the
possibility of describing local conditions in a
chemical reactor, thus representing the process
that eventually leads to reactor outlet conditions.
Mathematical representation consists of differ-
ential equations based on balance equations for
individual compounds and energy, including rate
expressions for chemical reactions (e.g., Eqs. 14
– 18) and transfer of mass and heat. Because ki-
netic models provide the most detailed descrip-
tion of gasification reactors, they require a large
number of parameters (activation energies, Ar-
rhenius factors, mass- and heat-transfer parame-
ters, etc.). Some parameters depend on feedstock
characteristics and can be determined experi-
mentally only with difficulty. Typical results of
kinetic models are temperature and component
concentration profiles in axial and radial direc-
tions. Examples of kinetic models can be found
for moving-bed [66, 72], fluidized-bed [73, 74],
and entrained-flow gasifiers [75, 76].
4.3. Characterization of Solid
Feedstocks for Gasification
An overview of the molar ratios of carbon: hy-
drogen: oxygen for solid feedstocks is presented
in Figure 23. Table 15 lists typical analytical
data and Table 16 gives an overview of char-
acteristic properties of different solid biomass
and waste materials. Some of the most important
properties that characterize solid carbonaceous
materials are discussed briefly in the following.
The significance of these properties depends on
the type of gasification process.
Moisture Content. Solid carbonaceous ma-
terials have moisture contents ranging from <
5 % (petroleum-derived residues and anthracitic
coals) up to about 50 % (lignitic coals, peat,
and wood). Moving-bed gasifiers can accommo-
date the highest moisture content (ca. 35 %) be-
cause the feedstock is dried in the gasifier by
60 Gas Production
Table 15. Data from typical solid feedstocks for gasification
Delayed coke Anthracitic coal Bituminous coal Lignitic coal Wood Municipal
(Ruhr) (Pittsburgh) (North Dakota) (redwood) solid
waste
Analysis as-received, wt %
C 82.6 88.6 75.4 48.7 35.8 47.6
H 3.1 3.2 2.2 3.0 4.1 6.0
O 0.2 3.3 8.1 14.6 29.7 32.9
N 1.6 0.1 1.2 0.6 0.1 1.2
S 3.4 0.9 2.2 0.2 0.1 0.3
Ash 0.4 2.9 6.5 6.6 0.2 12
Moisture 8.6 1.0 1.4 26.1 30.0 20
Va 1000 30 b 30 b 30 b 15 n.a. c
Ni a 220 20 b 20 b 20 b 15 n.a. c
Molar ratio
H/C 0.46 0.43 0.83 0.74 1.37 1.51
O/C 0.002 0.03 0.08 0.22 0.62 0.58
Volatile matter, wt % 10.2 5.6 38.0 27.8 58.1 59.5
Fixed carbon, wt % 80.8 90.5 54.1 39.5 11.7 8.5
Reactivity e relative to
bituminous coal 0.29 0.48 1.00 5.90 3.93 n.a. c
Ash softening tempera-
ture e , ◦ C 1155 1240 1260 1240 1150 n.a. c
Grindability, HGI f 50 – 100 50 60 60
General characteristics wide distribution of particle-size distribution depends on mining – cutting and
particle size, varies preparation/beneficiation
with cutting
procedure
a
Parts per million (by weight).
b
Typical value for coal.
c
n.a. = not available.
d
Gasification rate in CO2 (standard conditions).
e
Oxidizing conditions.
f
HGI = hard growth index.

Table 16. Characteristic properties of nonconventional solid feedstocks for gasification

Reactivity Moisture Inorganics Inorganics Inorganics Fixed carbon Volatiles Critical
content content composition melting temp. content content compounds
Biomass
Wood high high low Fe, Al, Si, Ca low low high
Waste wood high low varying varying low low high insecticides
pesticides
Energy crops high high moderate Si low low high
Agriculture high low low to high Si, Na, K low low high
waste
Sewage sludge high high high Si, Al, Fe, Ca, normal low high Hg, Cd, Pb,
P Cu, Cl, (N)
Waste materials
Municipal waste high varying medium to Si, Ca, Al, Fe normal low high Cl, F, Zn, Pb,
high Cu, Cr, S, Hg
Hazardous waste varying varying varying Si, Fe varying low varying Zn, Cu, Ba, Sn
Used tires low low Zn
Petroleum residues
Coke low low moderate low high low Ni, V
Hydrogenation low low medium medium high low Ni, V
residue *
* Example: Veba Combi Cracking (using lignite coke as additive).

exiting product gas. Entrained-flow and molten-
bath gasifiers generally require that the mois-
ture content be adjusted by predrying to maintain
free-flowing behavior during crushing, convey-
ing, and charging to the gasifier. Fluidized-bed
processes can cope with higher moisture con-
tent which, however, in any case leads to lower
process efficiencies.
Figure 23. Molar ratios C−H−O of feedstocks for
gasification
Ash Content. Ash is present in petroleum-
derived residues and wood in very low amounts
(< 1 %) and in coals from 1 to > 50 %. For gasi-
fication, ash should be at a minimum because
of the following reasons. High ash content is
detrimental to carbon conversion. It furthermore
must be heated to the gasifier outlet temperature,
which leads to heat losses. In addition, provision
must be made for withdrawing ash from the sys-
tem, which increases in complexity and cost with
increasing operating pressure. An exception is
the dry ash moving-bed gasifier which can cope
with high ash content (up to ca. 50 %) and uti-
lizes sensible heat in the exiting ash to preheat
the gasifying medium.
Ash fusion behavior is significant because in
some gasification processes the ash must remain
solid for removal (moving-bed nonslagging and
fluidized-bed processes), whereas in others it is
removed as a liquid slag (moving-bed slagging,
entrained-flow, and molten-bath processes). Fu-
sion temperature, therefore, must be thoroughly
Gas Production 61
taken into account in the design and operation
of gasifiers. Ash composition must be consid-
ered when selecting materials of construction,
particularly for slagging gasifiers. Ash can vary
in character from acidic to basic and can contain
elements such as iron, which may separate or
require special handling. Also, in slagging oper-
ation addition of reagents such as fluxes may be
desirable to improve flow characteristics of the
slag or to adjust its chemical behavior.
Ash can be beneficial when particular con-
stituents like potassium enhance the kinetics of
gasification, tar cracking, or other reactions.
Volatile Matter. Volatile matter refers to
gas, tar, oil, and phenolic compounds formed by
pyrolysis reactions of the feedstock. The yield of
these volatile products determines the remain-
ing amount of char that must be gasified in (rel-
atively slower) gas – solid reactions. Pyrolysis
product distribution depends strongly on feed-
stock characteristics and, to some extent, on re-
action conditions during pyrolysis (temperature,
heating rate, pressure, ambient gas composition,
particle size [51]).
Fixed Carbon. The residual char remaining
after pyrolysis contains the fixed carbon that
must be gasified in gas – solid reactions with
steam, hydrogen, carbon dioxide, air, or oxy-
gen. Because these gas – solid reactions are en-
dothermic for most gasification processes, the
specific heat requirement per unit mass of feed-
stock (which in autothermic processes means
specific oxygen or air consumption) depends on
the amount of fixed carbon in the feedstock. Of
the different feedstocks presented in Table 15,
wood and municipal solid waste have the low-
est value of fixed carbon, whereas delayed coke,
petroleum-derived residue from a high-severity
coking process, and anthracitic coal have the
highest values.
Caking Behavior. Caking and swelling oc-
cur with certain coals, a phenomenon related
to pyrolysis reactions. Certain bituminous coals
with a high content of volatile material become
fluid, and the particles may adhere together and
swell. Other coals with similar volatile mat-
ter content may retain the original shape, with
individual pieces caking together weakly. Still
other solid carbonaceous materials (e.g., lig-
62 Gas Production
nitic coals) can disintegrate during pyrolysis into
small pieces. Accordingly, feedstocks are re-
ferred to as strongly or weakly caking or non-
caking. Fluidized-bed processes tend to be sensi-
tive to strongly caking coals, whereas entrained-
flow, molten-bath and moving-bed processes
(with sophisticated mechanical stirrer systems)
can generally accept feedstocks with caking
properties.
Reactivity. Solid carbonaceous materials
and their residual char from pyrolysis exhibit
major variations in their reactivity to steam, hy-
drogen, carbon dioxide, and oxygen. This can
be attributed basically to three factors [77]:
1) Concentration of active sites (i.e., carbon
atoms located at the edges of crystallites or
building blocks);
2) Diffusional limitations on how rapidly reac-
tive gas molecules can reach active sites; and
3) Presence of catalytic inorganic impurities.
In technical gasification processes, reactivity
affects the temperature level at which the gasi-
fier must be operated to ensure acceptable car-
bon conversion. As a consequence, specific heat
requirements (i.e., oxygen or air consumption
in autothermic processes) are related to feed-
stock reactivity, to an extent dependent on the
particular type of process. For example, low re-
activity in combination with low ash fusion tem-
perature may be prohibitive for dry ash removal
gasification processes (e.g., fluidized-bed pro-
cesses). Highly reactive feedstocks are particu-
larly suited for methane production because low
operating temperatures favor the formation of
methane according to chemical equilibrium.
Of the feedstocks in Tables 15 and 16, wood,
biomass waste, and lignitic coal are the most re-
active, whereas petroleum-derived residues and
anthracitic coal have the lowest reactivity.
Particle-Size Distribution. The particle-
size distribution of a given carbonaceous ma-
terial depends on its origin and characteristics:
(1) system of mining (for coals), (2) type of cok-
ing process (for petroleum-derived residues),
(3) kind of cutting (for wood), (4) kind of pre-
treatment (for waste materials), (5) mechanical
strength, and (6) method of preparation and
transport. For example, strip-mined bituminous
coal may contain up to 30 % fines (< 3 mm)
whereas heavily mechanized deep-mined coal
may have 40 % or more, and strip-mined lignite
can reach 60 % [55].
In moving-bed gasifiers, relatively coarse
feedstock particles (3 – 50 mm) are preferred.
The acceptance of fines is limited. Develop-
ments have moved, however, toward acceptance
of a greater proportion of fines, either as agglom-
erates or by direct injection of fines into the gasi-
fier. Fluidized-bed, entrained-flow, and molten-
bath processes generally require pretreatment
steps such as drying, crushing, and grinding
to achieve an optimum feedstock size distri-
bution. Coal mining techniques that result in
high fines production offer an advantage in this
case, because they help reduce costs of the coal
preparation plant necessary for fine coal pro-
cesses. Where a grinding step is needed, feed-
stock grindability is an important property that
affects the kind and cost of equipment.
4.4. Moving- or Fixed-Bed Processes
In moving-bed gasifiers (also called fixed-bed
gasifiers), the gasifying medium passes through
a bed of granular or lump fuel. Figure 22 A
shows a nonslagging, countercurrent version,
which exhibits excellent thermal efficiencies be-
cause outgoing ash heats the incoming gases and
outgoing product gas heats the incoming solid
feedstock. The long residence times of solid par-
ticles moving through the bed (typically 1 – 2
h), together with the temperature profile of the
countercurrent system, allow high carbon con-
version efficiencies.
Tables 17 and 18 contain information on se-
lected moving-bed gasification processes and
typical performance data with coal and petro-
leum-derived residues as feedstocks. Dry ash
and slagging pressure gasifiers are shown as ex-
amples in Figures 24 and 25.
In countercurrent moving-bed gasifiers, the
solid fuel descends through four not distinctly
separate zones with varying temperatures (Fig.
22 A) and gas compositions, where the chemical
reactions outlined in Figure 18 can occur.
Drying and Pyrolysis Zone. Raw feedstock
comes in contact with hot product gases, and
moisture is driven off. Subsequently, pyrolysis
of the carbonaceous material occurs to yield
gaseous products and char.
 Gas Production 63
Table 17. Selection of moving-bed gasification processes a
Process name British Gas – Lurgi Lurgi pressure Wellman Wellman Imbert Thermoselect
(BGL) slagging gasification Galusha
gasifier
Licensor or contributor b British Gas Corp., Lurgi Wellman Dravo Imbert Thermoselect
Lurgi Thermal Energietechnik S.A.
Systems
Feedstock coal, petroleum coke, coal, waste RDF c coal coal wood municipal solid
waste RDF c waste
Gasifying medium st/ox st/ox, st/air st/air st/air, st/ox air (downdraft) ox
Method of heat supply I/A I/A I/A I/A I/A I/A
Operating pressure, MPa elevated (2.0 – 3.0) elevated (2.0 – atmospheric atmospheric atmospheric atmospheric
10.0)
Condition of residue slag dry ash dry ash dry ash dry ash slag
Application of product gas FG, FG/IGCC, SG FG, FG/IGCC, FG FG FG FG
SG
Developmental status commercial commercial commercial commer-cial commercial commercial
Number of commercial-size 2 > 165 > 40 > 150 very high 3
gas generators
Reference [55, 78 – 80] [55, 83] [84] [78] [54, 87] [86]
a
For abbreviations, see Section 4.2.1.
b
in some cases historical.
c
RDF = Refuse-derived fuel.

Gasification Zone. Char from the pyrolysis

zone comes in contact with hot combustion prod-
ucts and steam from the zone directly below.
Char – gas reactions occur mainly with steam,
carbon dioxide, and to a lesser extent, hydrogen,
so that the overall reaction is endothermic.
Combustion Zone. The combustion zone
supplies heat for the gasification zone directly
above. The key reaction is that of carbon (in
the remaining char from gasification) with oxy-
gen to produce heat and carbon oxides. Here,
the temperature rises to a maximum, which
in nonslagging operation must be kept below
the fusion point of the ash by supplying steam
in excess of that required to gasify carbon. In
slagging operation, the steam supplied together
with oxygen only slightly exceeds that required
to gasify carbon. This results in temperatures
of 1500 – 2000 ◦ C, at which the ash melts and
drains off as a liquid slag.
Ash Zone. In dry ash removal gasifiers, the
ash bed, located at the bottom, heats the incom-
ing gasifying medium by direct heat exchange
and acts as a distributor.
Lurgi Pressure Gasification Process.A
widely used version of the moving-bed gasi-
fier is the Lurgi dry ash pressure gasifier (Fig.
24), which has been used commercially since
the 1930s. The main gasifier shell is surrounded
by a water jacket in which process steam is pro-
Figure 24. Schematic of Lurgi dry ash pressure gasifier
a) Coal lock; b) Drive; c) Scrubbing cooler; d) Stirrer;
e) Water jacket; f) Ash lock
64 Gas Production
Table 18. Typical performance data of moving-bed gasification processes, feedstocks: coal and petroleum-derived residues a
Process name British Gas – Lurgi Lurgi Wellman
Feedstock bituminous coal delayed coke bituminous coal lignite North bituminous coal bituminous coal bituminous coal
Pittsburgh South Africa Dakota Germany Germany
Size of gasifier demonstration demonstration commercial commercial commercial pilot commercial
Volatile matter, 34.1 8.9 20.6 26.9 31.7 23.8 32.0
wt %
Fixed carbon, 50.2 85.7 50.9 30.6 52.6 38.6 49.0
wt %
Moisture, wt % 5.0 3.6 10.0 36.3 3.0 5.0 7.0
Ash, wt % 10.7 1.8 18.5 6.3 12.7 32.6 12.0
C, wt % (daf b ) 83.6 92.6 80.6 73.9 82.3 83.6 75.1
H, wt % (daf) 5.7 3.8 4.0 5.2 5.1 6.0 5.9
O, wt % (daf) 6.8 0.2 13.0 18.9 9.4 6.8 16.5
N, wt % (daf) 1.6 1.4 2.1 1.0 1.3 1.1 1.3
S, wt % (daf) 2.0 2.0 0.2 1.0 1.8 2.3 1.1
Molar ratio
H/C 0.818 0.492 0.596 0.844 0.744 0.861 0.943
O/C 0.061 0.002 0.121 0.192 0.086 0.061 0.165
Fischer assay tar,
b
wt % (daf) 17.8 1.2 5.5 8.9 14.8
Feed throughput,
t/h (daf) b 10.5 8 23.8 25.1 13.0 6.0 2.5
Reactor 1.8 1.8 3.8 3.8 3.4 1.5 3.0
diameter, m
Operating 2.5 2.5 2.8 3.1 2.0 9.0 atmospheric
pressure, MPa
Gasifying st/ox st/ox st/ox st/ox st/air st/ox st/air
medium
Ratio of steam to 1.0 1.1 5.8 6.9 7.0
O2
Ratio of steam to 0.4 0.2
air
Crude gas
composi-
tion, vol %
CO2 3.0 1.0 27.8 32.0 10.0 30.2 4.0
CO 56.4 60.0 23.0 15.8 21.5 17.5 29.0
H2 28.0 30.0 28.6 39.8 20.0 35.0 16.0
CH4 7.1 3.0 9.1 11.8 3.5 16.5 2.0
Cn H m 0.4 0.2 0.4 0.8 0.8 0.8
N2 4.2 5.4 0.4 44.2 49.0
Crude gas yield,
m3 (STP)/t 2190 2640 2381 1980 3800 2075 4300
(daf b )
Tar – oil yield,
kg/t (daf b ) 42.0 63.7 33
Oxygen
consumption,
m3 /m3 (STP) 0.20 0.17 0.14 0.13 0.18
Air
consumption,
m3 /m3 (STP) 0.56
Cold gas 85.1 88.1 80.9 86.8 76.3 81.9 ca. 80
efficiency, c %
Reference [88] [89] [90], [91] [92] [93] [84]
a
For abbreviations, see Section 4.2.1.
b
daf = dry and ash free.
c
For definition, see Section 4.2.2.

duced. A coal lock hopper is mounted on top of A mechanical stirrer is included in some designs
the gasifier to feed the coal (typically 3 – 50-mm to allow the gasifier to handle caking coals. A
particles), and a motor-driven distributor is used motor-driven grate at the bottom of the gasifier
to spread incoming coal evenly over the coal bed. is used to withdraw the ash formed, which drops
 Gas Production 65

Figure 25. Schematic of British Gas – Lurgi slagging gasifier (syngas production from solid waste materials, based on [80])
a) Feed preparation (metal removal, drying, pelletizing); b) Gas purification and conditioning; c) Clean gas utilization (meth-
anol synthesis, combined cycle power generation); d) Air separation

into the ash lock hopper. Steam and oxygen (or tent of the product gas, because most of the con-
air) are introduced at the bottom of the gasifier densable pyrolysis products are cracked while
and distributed through the coal bed via the ro- passing through the combustion zone. A higher
tating grate. The grate supports the coal bed and tar content in the product gas does not cause
is continuously rotated to ensure constant, even a problem when a gas turbine is situated close
withdrawal of ash. Raw product gas leaves from to the gasifier since tars are kept in the vapor
the top of the gasifier (typically at 400 – 600 ◦ C) phase. An example of a wood gasification pro-
and flows through a scrubber – cooler where it is cess is given in Table 17. Moving-bed gasifiers
washed by circulating gas liquor. Further cool- for wood gasification are suited to small-scale
ing, cleaning, and conditioning of the gas must application (generally less than 200 kg of wood
be done according to the desired application. per hour). Performance data for a moving-bed
In the British Gas – Lurgi Slagging Gasifier, downdraft wood gasifier are given in Table 21.
a slagging version of the Lurgi gasifier, the ash
melts as a eutectic with potentially added flux to
form slag. The high temperature in the combus-
tion zone is a result of low steam oxygen ratios
in the gasifying medium. Molten slag is tapped
discontinuously through a taphole into a quench
vessel, where the slag granulates as it drips into
the quench water. One application of this process
is the production of synthesis gas from various
waste materials, as shown in Figure 25.
Compared to the dry ash process, the slag-
ging version has higher capacities per unit vol-
ume (see Fig. 32), has lower hydrogen carbon
monoxide ratios, and produces less aqueous con-
densate, tar, phenols, and hydrocarbons. These Figure 26. Types of moving bed gasifier for wood gasifica-
can be recycled and destroyed by gasification. tion
For gasification of wood, most moving-bed A) Countercurrent updraft; B) Cocurrent downdraft
processes apply the cocurrent (or downdraft)
system in which product gas flows through a For gasification of municipal waste together
hot zone before leaving the gasifier (Fig. 26). with other waste materials, practical experience
The advantage of this system is the low tar con- is available with pressurized moving-bed gasi-
fiers and with the new Thermoselect process (see
66 Gas Production
Table 21). In the latter case, raw municipal waste
is pyrolyzed before being gasified under slag-
ging conditions. In the case of moving bed gasi-
fication, pretreatment of the waste feedstock is
required (extrusion/pelletizing, see Figure 25).
Slagging operation ensures vitrification of the
residue containing the inorganic material in the
feedstock.
Some advantages of moving-bed gasifiers
are: (1) the technology is mature with many
commercial designs available, including pres-
sure operation; (2) the large fuel inventory pro-
vides safety, reliability, and stability; (3) the dry
ash gasifier can cope with high ash content feed-
stocks; (4) the gasifier may be banked for long
periods; (5) the carbon conversion efficiency is
high; (6) the thermal efficiency is high because
of countercurrent flow and thus the specific oxy-
gen consumption is low (see Fig. 33); and (7) the
capability for turndown is high.
Some limitations of moving-bed gasi-
fiers include (1) internal moving parts with
some mechanical complexity are employed;
(2) gasifier capacity is limited by gas flow rates
(see Fig. 32); (3) feedstock fines must be han-
dled separately (e.g., via agglomeration); (4) the
product gas contains tar, oil, phenols, and ammo-
nia, which require separation and cleanup sys-
tems; and (5) excess steam for temperature con-
trol leads to thermal losses and requires special
condensate treatment.
Besides the processes mentioned in Tables 17
and 18, other moving-bed processes exist, some
of which are of historical interest only: BCURA,
Chevron, Demag, Foster Wheeler, Gegas, Gas
Integrale, Grand Forks, Kellogg, KGN [81], Kil-
ngas [82], Leuna, Morgas, Otto, Pintsch, Riley
– Morgan, Wilputte, Woodall Duckham for coal
gasification [55, 58, 78], and various processes
for wood gasification [85, 94].
4.5. Fluidized-Bed Processes
Fluidized beds for gasification of solids are
characterized by linear velocities of gasifying
medium sufficient to lift the solid particles. This
requires smaller particle sizes than moving-bed
processes, typically in the 0.1 – 5-mm range
(Fig. 22 B). As a result of fluidization, the solid
particles move about randomly so that mixing
of solids within the bed approaches that of a
perfectly mixed reactor. Therefore, the solids
composition and the temperature of the bed are
nearly uniform, bed temperature being chosen
according to feedstock reactivity. The maximum
bed temperature is limited by the ash softening
and sticking behavior. The temperature of reac-
tor exit gases is about the same as that of the
bed; a heat recovery device is required for en-
ergy economy.
Tables 19, 20 and 21 contain information
on selected fluidized-bed gasification processes
and typical performance data with various feed-
stocks. The number of processes in these tables
reflects the fact that fluidized beds have been
favored in many recent process development
projects, mainly because they combine some ad-
vantages of moving-bed (e.g., large fuel inven-
tory) and entrained-flow (e.g., control of hydro-
carbon formation) gasifiers. In addition to the
processes listed, others combine fluidized beds
with various contacting methods, such as dilute
phase entrainment or moving bed. An example is
the Hygas gasification process. In Tables 19 and
20 the DMT process is listed as an example for
an allothermic process, with heat from an exter-
nal source (e.g., from a nuclear reactor or from
hot flue gas) introduced via heat exchange bun-
dles in the fluidized bed. These data are included
although presently there is little commercial in-
terest in the process.
Fluidized beds with gas velocities far above
the minimum fluidizing velocity (3 – 10 m/s),
called circulating or fast fluidized beds [95], are
also used for gasification. They operate at lower
bed densities and can thus cope with caking coals
without particle agglomeration or sticking.
Winkler Gasification Process. The Winkler
gasifier, the first commercially applied fluidized-
bed process, has been in service since the 1920s
for producing fuel and synthesis gases from coal
(Fig. 27). The coal feed inlet is located in the
lower part of the gasifier. Variable-speed screws
feed crushed coal (< 9 mm) into the gasifier.
Steam and oxygen (or air) are fed through noz-
zles located at several levels in the fluidized bed
which occupies only the lower third of the gasi-
fier; the remainder serves as a disengaging zone.
Secondary steam and oxygen injection occur
above the bed level to gasify unconverted carbon
leaving the bed, tars, and hydrocarbons. Heavier
particles drop through the fluidized bed and pass
into the ash discharge unit at the gasifier bottom,
 Gas Production 67
Table 19. Selection of fluidized-bed gasification processes; feedstocks: coal and petroleum-derived residues, wood, and biomass waste *
Process name DMT Foster Wheeler DMT High Lurgi CFB U-gas Winkler
(catalytic) (Ahlstrom) temperature
Winkler
Licensor or contributor ** DMT DMT Rheinbraun Lurgi IGT Davy McKee
Feedstock coal wood chips agriculture lignite, brown coal, wood, coal coal
forestry waste coal waste
Gasifying medium st air st st/air, st/ox st/air, st/ox
st/air, st/ox st/air, st/ox
Method of heat supply E I/A E I/A I/A I/A I/A
Operating pressure, MPa 4.0 2.0 0.3 – 2.0 1.0 – 2.5 < 0.2 < 3.5 < 0.4
Condition of residue dry ash dry ash dry ash dry ash dry ashdry ash (ag- dry ash
glomerated)
Application of product gas SG FG (GT) FG (GT, GM, FG, FG/IGCC, FG, FG/IGCC, FG, FG/IGCCFG,SG,H2
FC) SG SG
Developmental status development commercial development commercial commercial commercial commercial
Number of commercial-size gas ≥1 2 3 ≥8 ca. 70
generators
References [96, 97] [98] [99] [78, 102, 108] [89, 103, 104, [55, 78, 85, [55, 78, 110]
109] 105]
* For abbreviations, see Section 4.2.1.
** In some cases historical.

whereas lighter particles are carried up through
the bed with product gas. Coal residence time
is 20 – 30 min, based on coal feed rate. Carbon
conversion is limited by feedstock reactivity and
continuous loss of carbon with the ash.
ates at elevated pressure (up to 1.0 MPa) and
slightly increased temperature, i.e., conditions
that considerably improve process efficiency and
gas quality with respect to the requirements of a
synthesis gas.

Figure 28. Schematic of U-Gas gasifier

U-Gas Gasification Process. A pressurized

Figure 27. Schematic of Winkler gasifier
a) Coal screw; B) Ash screw
A modification of the atmospheric Winkler
gasification process has been developed (high-
temperature Winkler process, HTW): It oper-
version of a fluidized-bed gasifier with con-
trolled ash agglomeration is shown in Figure 28.
The U-gas gasifier is a vertical cylinder with two
cyclones for returning elutriated fines to the bed.
A sloping grid at the bottom serves as the air and
steam distributor and the agglomerated ash out-
let. Noncaking coals can be fed directly to the
gasifier from the crusher (particle size < 6 mm).
Caking coals may require pretreatment by con-
68 Gas Production
Table 20. Typical performance data of fluidized-bed gasification processes; feedstocks: coal and peat a
Process name DMT High-temperature Winkler U gas Winkler
Feedstock bituminous brown coal peat bituminous lignite lignite
coal coal
Size of gasifier pilot commercial commercial pilot, commercial commercial commercial
Volatile matter, wt % 12.2 44 – 46 57 – 61
Fixed carbon, wt % 68.2 37 – 40 20 – 24
Moisture, wt % 1.2 12 (10 – 25) 15 (12 – 18) 8.0 8.0
Ash, wt % 18.4 4 (2 – 18) 4 (3.5 – 4.5)
C, wt %, (daf e ) 86.9 69 60 71.1 71.2
H, wt % 4.0 5.0 5.0 5.5 4.8
O, wt % 4.9 25 31 18.9 20.2
N, wt % 2.0 0.9 2.8 0.9 2.2
S, wt % 2.2 0.1 0.2 3.8 1.6
Molar ratio
H/C 0.559 0.870 1.200 0.920 0.818
O/C 0.042 0.272 0.387 0.199 0.213
Feed throughput,
t/h (daf e ) 22 21 1–5 29 41
Reactor diameter, m 2.71 2.4 6 6
Operating pressure,
MPa 4.0 1.0 1.0 1.6 – 2.4 0.105 0.105
Gasification
temperature, ◦ C 830 950 950 ca. 1000 815 – 1200 815 – 1200
c
Gasifying medium st st/ox st/ox st/air st/air st/ox
Ratio of steam to O2 1.43
Ratio of steam to air ca. 0.3 0.06
Crude gas composition, vol %
CO2 22.3 22.8 21.3 9.9 7.7 19.5
CO 13.7 35.7 31 19.6 22.5 36.0
H2 56.2 35.9 29.7 17.5 12.6 40.0
CH4 7.8 4.9 5.6 3.4 0.7 2.5
Cn Hm 0.1 0.1
N2 0.6 12.3 48.9 55.7 1.7
Crude gas yield,
m3 (STP)/t (daf e ) 2000 2100 3596 3058 1760
Tar – oil yield, kg/t (daf e )
Oxygen consumption,
m3 /m3 (STP) 0.19 0.19 0.14 – 0.24
Air consumption,
m3 /m3 (STP) 0.43 – 0.76
Cold gas efficiency, d % 80 73 71 – 79 61.9 74.4
Carbon conversion, d % 95 94 92 96 – 98 83.0 81.0
Reference [96, 97] [102] [102] [105] [55, 56]
a
For abbreviation, see Section 4.2.1.
b
Predried.
c
Gasification with oxygen-enriched air.
d
For definition, see Section 4.2.2.
e
daf = dry and ash free.

tact with air in a second fluidized bed operating
at gasifier pressure and 370 – 430 ◦ C. Here, an
oxidized outer layer forms on the coal particles
and prevents agglomeration and possible block-
age in the gasifier.
Coal is gasified with a mixture of air (or oxy-
gen) and steam in a single-stage fluidized bed.
Residence time of the particles is ca. 45 – 60
min. The fluidizing velocity is about 1 m/s. The
key to gasifier operation is the agglomeration
and separation of low-carbon ash from the bed.
This is accomplished by keeping the tempera-
ture near the gasifying medium inlet close to the
softening point of the ash particles. Thus, ash
particles preferentially stick together, and the ag-
glomerates grow until they are heavy enough to
move downward and fall out of the fluidized bed.
The fluidized-bed system is particularly at-
tractive for gasification of wood and other
biomass because it allows greater feedstock flex-
ibility (e.g., with respect to particle size) and
easier scaleup than moving-bed gasifiers. There-
 Gas Production 69
Table 21. Typical performance data of wood, biomass, and waste gasification processes a
Process name Imbert Lurgi/SVZ Foster Lurgi CFB Thermoselect
Wheeler
Ahlstrom
System moving bed grate gasifier fluidized bed fluidized bed moving bed
downdraft
Feedstock wood RDF/various wood chips wood bark wood waste lignite municipal
waste/coal combustion solid waste b
mix residue
Size of gasifier commercial commercial commercial commercial commercial
Volatile matter, wt % (70)
Fixed carbon, wt % (15)
Moisture, wt % 10 – 20 8 – 10 19 10 20 – 30
Ash, wt % 2–5 2 78 20 – 30
Feed throughput, t/h (daf e ) ca. 10 3.5 – 4.5 mix mix 1.5 – 5
(70 – 100 MWth)
Reactor diameter, m 3.6
Operating pressure, MPa atmospheric 2.4 1.8 atmospheric atmospheric atmospheric
Operating temperature, ◦ C f f
950 – 1000 ca. 800 900 – 950 600 – 1200
Gasifying medium air st/ox air air air ox
Ratio of steam to O2 – – – 0.0
Ratio of steam to air 0.0 0.0 0.0 0.0 –
Crude gas composition, vol %
CO2 10.0 31 – 35 12 15 22 – 27
CO 20.0 15 – 22 16 15.4 35 – 39
H2 19.0 29 – 35 13 14.8 32 – 36
CH4 1.5 9 – 13 3 4.2 < 0.1
Cn H m 2.0 < 0.1
N2 50.0 44 39.6 3–4
Crude gas yield, m3 (STP)/kg (daf e ) 2000 – 3000 1588 – 1926
Oxygen consumption, m3 /m3 (STP) – 0.45 – 0.52 c
Air consumption, m3 /m3 (STP) (0.48) g –
Cold gas efficiency, d % > 70
Carbon conversion, d % 93 > 96
Reference [115] [80] [98] [116] [103] [86]
a
For abbreviations, see Section 4.2.1.
b
Without pretreatment.
c
With natural gas as additional fuel (ca. 135 m3 (STP)/t daf).
d
For definition, see Section 4.2.2.
e
daf = dry and ash free.
f
Temperature distribution.
g
Estimated value.

fore, several fluidized-bed concepts have been
proposed and developed; a selection is presented
in Table 21. As an example, Figure 29 shows
a flow diagram for fuel gas production from
biomass and waste feedstocks in a circulating
fluidized-bed reactor integrated in a cement pro-
duction plant. The feed material is fed to the
lower part of the gasifier via a screw feeder. Air
as gasifying agent is injected at the bottom. Be-
cause of excellent heat-transfer conditions, the
temperature is uniform throughout the reactor
and is high enough to convert the tarry and oxy-
genated pyrolysis products. Typical plant capac-
ities for fluidized-bed wood and waste gasifiers
are in the range of several tons per hour. The
product gas is particularly suitable as feedstock
for boilers, lime kilns, gas engines, and gas tur-
bines.
Advantages of fluidized-bed gasifiers are: (1)
commercial designs are available; (2) the tech-
nology is less complex than that of moving beds
and does not involve moving parts; (3) the large
fuel inventory provides safety, reliability, and
stability; (4) a variety of particle sizes can be
handled; (5) the amount of tar and phenols is
low; (6) gas composition is steady due to uni-
form conditions in the bed; and (7) moderate
gasification temperatures can be used.
Limitations of fluidized bed-gasifiers include
the following: (1) capacity flexibility is lim-
ited by entrainment at high gas velocities;
(2) the inventory of solid carbon is lowered
70 Gas Production
Figure 29. Flow diagram of a circulating fluid bed process for the production of fuel gas from biomass and waste feedstocks,
integrated in a cement production plant, based on [103].
by the high content of inert material in the
bed; (3) caking coal may require pretreatment;
(4) conflicting temperature requirements exist
for low-reactivity feedstocks with low-softening
point ash; (5) inevitable loss of carbon in ash
occurs due to uniform solids composition of the
bed; (6) the turndown range is limited by the gas
velocity required to maintain fluidization.
Besides the processes mentioned in Tables 19
20 21, other fluidized-bed processes are BASF
– Flesch – Demag, Battelle – Union Carbide,
Hydrogasification, BCR, CGT, CO2 -Acceptor,
Electrofluidic process, Exxon catalytic pro-
cess, Hydrane, Hydrogasification (HKV), Hy-
gas, KRW, Synthane, Tosco, University of
Wyoming, West Virginia University, Winkler –
Flesch for coal or petroleum coke [55, 58, 117,
119], IGT’s RENUGAS and various other pro-
cesses for wood and waste gasification [54, 94,
118].
4.6. Entrained-Flow Processes
In entrained-flow gasifiers, solid particles are
carried or entrained by the reacting gases. Thus,
solids and gases move in the same direction with
approximately the same velocity. To achieve
this, the particles must be smaller than in other
systems (typically 70 % < 0.1 mm). This, to-
gether with high temperature (see Fig. 22 C),
allows gasification rates high enough to ensure
acceptable carbon conversion during the short
solids residence time in the gasifier (a few sec-
onds).
The reactants (e.g., coal, oxygen, and steam)
are typically introduced into the gasifier at high
velocity through one or more burners or noz-
zles. The burners can be oriented in many dif-
ferent ways, for instance, tangentially, radially
opposed, and axially. Gasifier performance is af-
fected to a large degree by the flow characteris-
tics and mixing efficiency of the burners. The
solid feedstock is either injected in the form of
a water slurry or as dry particles.
Flame temperatures at the burner outlets can
be as high as 2000 ◦ C. This results in extremely
rapid conversion of feedstock particles and de-
struction of virtually all higher hydrocarbons.
Outside the immediate flame region, heat losses,
further mixing with steam, and endothermic re-
actions combine to lower the gas-phase temper-
ature. Because of the high reaction temperature,
oxygen consumption is usually greater than for
other gasification systems (see Fig. 33). A sig-
nificant portion of the feedstock ash melts be-
cause of the high reaction temperature and is
removed from the reaction zone as liquid slag.
Tables 22 and 23 contain information on se-
lected entrained-flow gasification processes and
typical performance data with coal or petroleum-
derived residues as feedstock. Figures 30 and 31

show, as examples, a Koppers – Totzek gasifier
and a scheme of the Texaco coal gasification pro-
cess with gas cooler mode.
Figure 30. Schematic of Koppers – Totzek gasifier
a) Gasifier; b) Waste heat boiler; c) Slag quench tank
Koppers – Totzek Gasification Process. The
two-headed Koppers – Totzek gasifier (Fig. 30)
is horizontal and ellipsoidal in shape, with two
heads mounted on the ends. A waste-heat boiler
is mounted on top to recover heat from the hot
effluent gases. The usual waste-heat boiler sys-
tem, which produces high-pressure steam as a
byproduct of the process, is a radiant surface
boiler followed by a fire tube boiler. The gasifier
shell is protected from the high gasification tem-
peratures by a castable refractory lining. Coal
is dried to 2 – 8 % moisture content (depending
on coal rank) and simultaneously pulverized to
70 – 90 % below 80 µm. A variable-speed screw
feeder feeds the pulverized coal into a mixing
nozzle, where a premixed stream of oxygen and
steam is introduced. Steam and oxygen entrain
the pulverized coal, and the coal – steam – oxy-
gen mixture is injected into the gasifier burn-
ers at injection speeds above the speed of flame
propagation to prevent flashback. Two adjacent
burners on each head improve turbulence be-
havior and provide a safety feature to ensure
Gas Production 71
continuous ignition if one burner is temporarily
blocked. Coal particles are gasified in approx-
imately 1 s or less, producing a temperature in
the flame zone of ca. 1900 ◦ C. Heat losses and
endothermic reactions cool the gas mixture to ca.
1300 ◦ C. Ash in the coal is liquefied because the
gasifier temperature is maintained above the ash
fusion temperature. Most of the ash flows down
the gasifier walls as molten slag and drains into a
slag quench tank. Part of the ash leaves the gasi-
fier as fine slag particles entrained in the exit
gas. Pressurized modifications of the Koppers
– Totzek process are the Prenflo and the Shell
gasification processes (the latter jointly devel-
oped by Shell and Koppers), both using dry solid
particles as feed.
TTexaco Gasification Process. The exaco
coal gasification process (based on experience
with oil gasification; see Section 3.2.2) uses a
pressurized version of an entrained-flow reactor
and a slurry system (Fig. 31). The gasifier is
a vertical, cylindrical vessel with a refractory-
lined upper portion where solid feedstock reacts
with steam and oxygen. Hot product gas is
cooled upon leaving the gasifier, either by di-
rect quenching with water, resulting in internal
steam production, or by indirect cooling in gas
coolers with external high-pressure steam gen-
eration. The mode of operation is determined
by the method of downstream processing and
by the end use of the product gas. The quench
mode is generally selected for the production
of hydrogen or ammonia; carbon monoxide in
the raw product gas reacts with steam in a car-
bon monoxide shift step to produce additional
hydrogen. The gas cooler mode of operation is
selected for applications that do not require car-
bon monoxide conversion (e.g., syngas for oxo
synthesis or clean fuel for power generation).
The solid gasifier feed is processed through two
stages of dry grinding (the second under in-
ert atmosphere) and pneumatically conveyed to
slurry mix tanks where it is mixed with water
to form a pumpable slurry (slurry solids loading
50 – 70 %). The slurry is fed continuously to the
top of the gasifier by a positive displacement
pump.
Advantages of Entrained-Flow Gasifiers.
Among the advantages of entrained-flow gasifi-
cation processes are: (1) commercial designs are
available; (2) the gasifier has no moving parts
and a simpler geometry than a fluidized bed;
72 Gas Production
Table 22. Selection of entrained-flow gasification processes *
Process name Koppers – Totzek Prenflo Shell Texaco DesTec (DW)
Licensor or contributor Krupp – Koppers Krupp – Koppers UhdeShell Texaco Dynegy
Uhde
Feedstock coal coal coal coal coal
petroleum coke petroleum coke (dry) petroleum coke (dry) petroleum coke petroleum coke,
(dry) (slurry) (slurry)
Gasifying medium ox (st/ox) ox (st/ox) st/ox st/ox ox
Method of heat supply I/A I/A I/A I/A I/A
Operating pressure, MPa atmospheric 3.0 2.0 – 4.0 < 8.5 < 1.5
Condition of residue slag slag slag slag slag
Application of product
gas FG,SG,H2 FG,SG,H2 ,FG/IGCC FG,SG,RG,FG/IGCC,H2 FG,SG,H2 ,FG/IGCC FG,SG,H2 , FG/IGCC
Developmental status commercial development development commercial commercial commercial
commercial
Number of commercial-
size gas generators ca. 80 1 ≥1 ≥5 ≥2
Reference [55, 78, 120] [78, 120, 124] [78, 121, 122, 125] [55, 78, 126 – 129] [123]
* For abbreviations, see Section 4.2.1.

Figure 31. Schematic of Texaco coal gasification process with gas-cooler mode
a) Mill; b) Slurry tank; c) Slurry pump; d) Gasifier; e) Radiation cooler; f) Lock hopper; g) Convection cooler; h) Gas scrubber;
i) Clarifier; j) Slag screen

(3) the gasifier has the highest capacity per unit
volume (see Fig. 32); (4) any type of coal may
be used without pretreatment; (5) no fines are
rejected; (6) the product gas is free of tar and
phenols (see Fig. 33); and (6) the slagged ash
produced is inert and has a low carbon content.
Limitations of entrained-flow gasifiers in-
clude: (1) combustor nozzles and heat recovery
in the presence of molten slag are critical de-
sign areas; (2) a small solids inventory requires
advanced control techniques to ensure safe, re-
liable operation; (3) pulverizing and drying of
surface moisture are required; and (4) the high
gasification temperature causes thermal losses,
necessitates higher quality construction materi-
als, and leads to increased oxygen consumption
(see Fig. 33).
Besides the processes mentioned in Tables 22
and 23, other entrained-flow processes are Bab-
cock Wilcox, BiGas, Combustion Engineering,
Foster Wheeler, GSP, and ORC for coal or pe-
troleum coke gasification [55, 131].
4.7. Molten-Bath Processes
In molten-bath gasification processes, solid
feedstock and gasifying agents are injected into
 Gas Production 73
Table 23. Typical performance data of entrained-flow gasification processes; feedstocks: coal and petroleum-derived residues a
Process name Koppers – Prenflo Shell Texaco
Totzek
Feedstock coal mixture of coal bituminous Texas lignite bituminous delayed coke
coal/ coal (Illinois coal (Illinois
petroleum no. 6) no. 6)
coke
Size of gasifier commercial commercial pilot pilot g pilot g pilot h pilot
Volatile matter, wt % 18.5 33 34 31 33.5
Fixed carbon, wt % 56 52 41 27
Moisture, wt % 1.0 b 9.4 6.0 16 c 33 c 13.0
Ash, wt % 20.2 24.5 8.8 9 9 11.1 0.5
C, wt % (daf f ) 79.7 84.7 81.5 77.0 72.0 78.1 90.7
H2 , wt % 4.6 4.0 5.4 6.0 6.0 5.1 3.9
O2 , wt % 13.5 4.7 10.1 11.0 19.0 11.6 0.9
N2 , wt % 1.8 1.9 1.9 1.4 1.2 1.3 2.6
S, wt % 0.5 4.7 1.1 4.3 1.0 3.8 1.9
Molar ratio
H/C 0.688 0.935 1.000 0.784 0.516
O/C 0.127 0.107 0.198 0.111 0.007
Feed throughput,
t/h (daf f ) 71 1.7 5.7
Operating pressure, MPa i 2.5 2.4 2.1 – 2.8
Gasification tempera-
ture, ◦ C 1870 > 2000 > 2000 > 1250
Gasifying medium st/ox st/ox st/ox st/ox ox ox ox
Ratio of steam to O2 0.196 0.14 0.04 0.080 0.0 1.0 d 0.75 d
Crude gas composition
(dry), vol %
CO2 6.9 3.8 1.9 2.0 4.6 20.7 13.3
CO 64.3 61.9 58.4 65.1 61.8 41.1 53.4
H2 27.1 22.5 26.2 30.5 32.4 36.6 31.8
CH4 0.1 0.1 0.1 0.1 0.02
Cn H m
N2 0.9 11.7 13.4 0.9 0.9 0.4 0.95
Crude gas yield,
m3 (STP)/t (daf f ) 2578 2230 2109 2029 2192 2667
Tar – oil yield,
kg/t (daf f )
Oxygen consumption,
m3 /m3 (STP) 0.30 0.30 0.297 0.294 0.321 0.304
Cold gas efficiency, e % 69.3 78.4 81.8 81 81 70.3
Carbon conversion, e % 90.0 99.3 99.3 99 94
Reference [55] [124, 130] [130] [122] [122] [128] [126]
a
For abbreviations, see Section 4.2.1.
b
Predried.
c
Before drying.
d
H2 O as water in slurry.
e
For definition, see Section 4.2.2.
f
daf = dry and ash free.
g
Commercial-scale data in [125].
h
Commercial-scale data in [129].
i
Exact pressure not always available, see also Table 22.

a hot liquid bath of molten slag, metal, or salt
(Fig. 22 D). The high temperature normally re-
quired to keep the bath molten promotes high
reaction rates, which are often enhanced by cat-
alytic properties of the melt. The material em-
ployed for the melt largely determines the char-
acteristics of each particular process. Slag acts
mainly as a heat-transfer medium but can some-
times have a catalytic effect. Iron is used as a
bath material because of its strong affinity for
sulfur, its high solubility of carbon in molten
iron, and because any iron oxide present in the
melt will donate oxygen. Molten salts, which are
generally less corrosive and have lower melting
points than molten metals, may strongly catalyze
the basic char – steam reaction, permitting prac-
74 Gas Production

tically complete gasification of some feedstocks

at relatively low temperature.
As an example, the Molten Iron Puregas
(MIP) Gasification Process uses an iron inven-
tory of 20 t for a coal throughput of 10 t/h. The
reactor is designed for gasification pressure up
to 0.3 MPa and is brick lined. It contains liquid
iron into which the feed coal is injected via an
inert carrier gas, as well as facilities for feeding
oxygen and other media that may be required
such as lime for adjusting the basicity of the
slag and steam for cooling the iron. Slag float-
ing on the surface of the iron bath is discharged
continuously and subjected to secondary treat-
ment. Product gas leaves the reactor at ca. 1400 –
1500 ◦ C and passes through a waste-heat recov-
ery system followed by a dust removal system.
Pilot-plant design enables optimum location of
feeding points, either at the top (top blowing) or Figure 32. Effect of pressure and type of gasification reac-
at the bottom (bottom blowing) of the reactor, tor on capacity per unit volume, based on published data,
to be investigated. This process draws on expe- feedstock: various coals
rience available from steelmaking technology. a) Moving bed dry ash; b) Moving bed slagging;
c) Fluidized bed; d) Entrained flow; e) Molten bath iron
Advantages of molten-bath gasifiers Among
the advantages of molten-bath gasifiers are
(1) the large fuel or heat inventory provides
safety, reliability, and stability; (2) the high-tem-
perature bath ensures safe ignition; (3) any grade 4.8. Underground Coal Gasification
of coal in a wide size range can be utilized (i.e., [135 – 138]
crushed run-of-mine coal); (4) no pretreatment
or pulverization is required for gasifier opera- The purpose of coal gasification in situ is to re-
tion; and (5) product gas contains no sulfur (re- cover the energy or chemical values of the coal
tained in molten bath) and no tar or phenols at without mining. Gaseous products may be uti-
high temperature. lized for electric power generation, manufacture
Limitations of molten-bath gasifiers include of organic chemicals, and synthesis of liquid or
the following: (1) cleanup of molten media (if gaseous fuels. Advantages of in situ coal gasifi-
required) is complicated; (2) capacity flexibility cation are the elimination of underground min-
is limited by melt entrainment in the product gas ing operations and, possibly, the utilization of
at high flow rates; (3) ash is removed as liquid coal in beds that cannot be mined profitably. In-
slag, leading to loss of sensible heat; (4) the cata- cluded among past attempts are projects in Eu-
lyst (if required) must be separated from ash for rope, the United States, and the Soviet Union.
recycle, and make-up catalyst must be added; Although details vary from project to project,
(5) the melt may be highly corrosive to refrac- mixtures of oxygen and steam (or air and steam)
tory at the gasifier temperature; and (6) bottom must always be admitted into a hot zone in the
blowing gasifiers require sophisticated cooling coal seam for gasification to occur, and raw prod-
systems for the tuyeres. uct gas must be withdrawn from the coal seam
Process variations include besides the Molten for surface processing to make the gas environ-
Iron Puregas Process (MIP) other processes for mentally and technically acceptable. The main
coal or petroleum gasification: Rummel [61], difficulties in underground coal gasification are
Rockgas Molten Salt [132, 133], Saarberg/Otto creating and maintaining adequate permeability,
[78], Atgas, Kellogg, Klöckner, Sun [55, 134]. maintaining and controlling the reaction zone,
minimizing the detrimental effects of fissuring
and channeling, and maintaining steady product

Figure 33. Characteristic temperatures of different gasification systems and correlation with selected performance data, based
on published data
a) Phenols; b) NH3 ; c) CH4 ; d) O2 -consumption
gas composition and yield. Despite past projects,
underground gasification of coal is not used
widely at present and is not expected to play
a significant role in the near future.
4.9. Environmental Aspects of
Gasification
Gasification offers a practical means of utilizing
coal, petroleum-derived residues, wood, or solid
waste material while at the same time meeting
stringent environmental control requirements.
Although the type and severity of environmental
control problem vary with gasification process,
routine commercial operations have demon-
strated successful cleanup of the most difficult
streams.
Air Emissions. Among the sulfur com-
pounds, reduced species (H2 S, COS, CS2 ) pre-
dominate in gasifier raw gases and can be re-
moved by a variety of processes (Chap. 5). Sul-
fur compound concentrations are higher in gasi-
fier gases than in combustion gases, which fa-
cilitates their removal. For example, synthesis
gas streams can be cleaned sufficiently for use
Gas Production 75
in processes that require almost total removal of
sulfur compounds because of the use of sulfur-
sensitive catalysts. In addition, studies indicate
that virtually complete control of sulfur in coal
gasification increases product cost only moder-
ately [53].
Particulates are routinely removed from syn-
thesis gas produced by coal gasification to be fed
to catalyst beds for chemical synthesis. In this
case, particulates are removed to a far greater
extent for catalyst protection than would be nec-
essary to comply with environmental require-
ments. Of greater concern are emissions from
feed lock hoppers or feed handling and storage
systems; these, however, can be controlled if the
equipment is designed properly.
Although nitrogen oxides are not formed to
any appreciable extent in the reducing atmo-
sphere of gasification, use of the product gas as
fuel for combustion could pose an NOx emission
problem due to nitrogen compounds in the gas.
However, well-cleaned product gas from gasi-
fication should yield an improvement over, for
example, the direct firing of coal.
Water Effluents. Gasification processes in
which raw gas leaves the gasifier at relatively
76 Gas Production
low temperature (moving bed) result in greater
requirements for wastewater treating because of
the tar and phenols produced, yet such waste-
water can be purified adequately by conven-
tional technology. For example, water effluent
streams from Lurgi gasifiers have been well con-
trolled on a large commercial scale at the Sasol II
complex (→ Coal Liquefaction) in South Africa.
Some gasification plants are designed for zero
discharge in arid areas where discharges might
seriously affect the quality of the receiving wa-
ter.
Solid Wastes. All coal-consuming processes
require the disposal of ash or slag resulting from
the mineral content of coal. Some concern has
been expressed that solid waste from gasifica-
tion might be declared hazardous because of its
leaching characteristics. However, leaching of
gasification waste generally results in lower con-
centration of metals than leaching of power plant
ash, which has not been classified as hazardous.
5. Gas Treating
Gas treating described in this chapter is often
preceded by a separation stage for condensates
obtained from cooling stages immediately fol-
lowing gas production (see Chap. 6). An over-
all gas treating sequence is described in Section
7.2.
Objectives. The method of gas treating is
determined essentially by the following condi-
tions:
1) origin (i.e., state and composition of the raw
gas) and
2) utilization (i.e., specifications for the treated
gas).
As described in previous chapters, the com-
position of raw gases differs considerably de-
pending on the mode of production; this applies
also to raw gas pressure and temperature (see
Table 24).
Requirements for the treated gas are mani-
fold. They are more or less stringent depending
on whether the gas is to be used as a feedstock
for synthesis or as fuel gas. Generally, no spe-
cial requirements exist for fuel gas composition
as long as the limits for calorific value and den-
sity are met (see Chap. 8). Purity is specified
with a view to avoiding corrosion and deposits
in the piping system or toxicity.
When syntheses follow downstream of gasifi-
cation, the stoichiometry of the reaction requires
a very specific composition, and the catalysts,
which are generally sensitive, set very exacting
standards for purity of the reactants. In addition,
economic aspects must be considered concern-
ing the inerts contained in the gas, which unnec-
essarily reduce the partial pressure of reactants
and tend to concentrate in recycle processes so
that a considerable amount of purge gas must be
branched off.
Stoichiometric Conditions. Most syntheses
of basic chemicals in very large quantities start
from hydrogen and/or carbon monoxide, in con-
junction with further reactants if necessary. The
ratio of hydrogen to carbon monoxide offers a
simple characterization (see Table 25).
Purity. Sulfur compounds, which are severe
respiratory and catalyst poisons and may cause
dangerous corrosion, are the subject of almost all
purity specifications. The content of hydrogen
sulfide (measured as sulfur) is generally limited
to 2 mg/m3 in long-distance pipeline systems.
For syntheses, particularly those using sensitive
copper catalysts, the permissible concentration
is much lower: e.g., for the low-pressure meth-
anol process, 0.1 ppm of total sulfur, measured
as hydrogen sulfide.
In some syntheses, oxygen compounds are
also undesirable: thus a content of
O2 +CO2 +2 CO<20 ppm
is usually required for ammonia synthesis (→
Ammonia). For reasons of corrosion, the oxygen
content in gas grids is limited to 0.5 – 3 %. Ni-
trogen oxides are also undesirable because they
may form unwanted or dangerous compounds
with unsaturated hydrocarbons. This applies not
only to syntheses but also to gas piping systems
and cryogenic gas treatment processes (→ Cryo-
genic Technology; → Natural Gas). In view of
the high process pressures, the nitrogen content
of hydrogen used for hydrocracking is often lim-
ited to avoid formation of ammonia.
A number of other impurities, such as hydro-
gen cyanide, organic acids (e.g., formic acid),
 Gas Production 77
Table 24. Typical raw gas data
Raw material: Coal Vacuum residue Natural gas
Example: 1 2 3 4 5 6
Production process: Koppers – Lurgi Pressure Shell Gasification Texaco Tubular reformer
Totzek Gasification Process Gasification
Process
ex gasifier downstream of downstream of upstream of CO downstream
scrubber CO shift shift of CO shift
Pressure, MPa 0.105 2.9 5.4 8.5 2.2 2.1
Temperature, ◦ C 45 45 35 35 350 230
Water dew point, ◦ C 45 45 35 35 170 162
Analysis, vol %
H2 28.7 43.2 45.9 63.0 76.1 78.3
CO 57.0 11.6 48.6 1.8 10.6 0.4
CH4 0.1 10.7 0.5 0.3 3.3 3.0
C2+ 1.0
N2 + Ar 1.4 0.3 0.2 0.1
CO2 12.6 32.9 4.0 34.2 10.0 18.3
H2 S 0.2 0.3 0.8 0.6
COS, ppm 300 150 500 10
Other components O2 , SO2 , O2 , C m Hn , O2 , HCN, NH3 NH3
HCN, NH3 HCN, NH3

Table 25. Typical hydrogen – carbon monoxide stoichiometric numbers for a few basic chemicals
Product Acetic acid a Oxo alcohols b Direct Fischer – Methanol e Ammonia
reduction c Tropsch d
CH2 /CCO 0 – 0.02 1.0 – 1.2 1.3 – 1.5 1.6 – 2.3 2.0 – 2.3 >105
Additional reactants methanol propylene iron oxides CO2 CO2 N2 (=1/3 H2 )
a
Monsanto process (→ Acetic Acid).
b
BASF and Ruhrchemie process; Shell process: 1.6 – 1.8.
c
Midrex process.
d
Lower range for fixed-bed synthesis (ARGE);
upper range for
 Synthol

(SASOL).
e
The reaction is reflected more accurately by CH2 −CCO2 / CCO +CCO2 (→ Methanol).

or unsaturated and higher boiling hydrocarbons, ity of industrial processes, this carbon monoxide
are normally not included in purity specifica- content is higher than that required for synthesis.
tions for synthesis processes because they are Exceptions include, for instance, the synthesis of
already undesirable in upstream process stages oxo alcohols and of acetic acid from methanol
of synthesis gas production. and pure carbon monoxide.
The total content of inerts (N2 , Ar, CH4 ), The following are typical examples of com-
which in most cases are not dangerous to synthe- mercial processes in which carbon monoxide in
sis but undesirable for economic reasons, must raw synthesis gas is partly or largely converted:
often be < 2 %.
1) Adjustment to the desired hydrogen: car-
To meet all these requirements, several pro-
bon monoxide ratio in carbon monoxide-rich
cess stages are necessary for gas purification
gases, which are formed, for instance, by par-
or separation. They include catalytic processes
tial oxidation (e.g., methanol synthesis);
(CO shift conversion, COS conversion, metha-
2) Conversion of toxic carbon monoxide to car-
nation; see Sections 5.1, 5.2, 5.3), as well as
bon dioxide (e.g., town gas); and
absorption, adsorption, and other fractionation
3) Production of hydrogen from steam used for
processes (Sections 5.4, 5.5, 5.6, 5.7, 5.8).
the carbon monoxide shift reaction (e.g., hy-
drogen production, ammonia synthesis).
5.1. Carbon Monoxide Shift Conversion
Processes for the manufacture of synthesis gas 5.1.1. Fundamentals
from hydrocarbon feedstocks produce mixtures
of hydrogen, carbon dioxide, methane, and vary- The water gas shift equilibrium among carbon
ing amounts of carbon monoxide. For the major- monoxide, carbon dioxide, hydrogen, and steam
78 Gas Production
depends on temperature but is almost indepen-
dent of pressure in the industrial range (elevated
pressures up to 7.0 MPa).
Carbon monoxide shift conversion is an
exothermic reaction:
0
CO+H2 O
H2 +CO2 ∆HR = −41.2 kJ/mol
The equilibrium constant is described by
pH2 ·pCO2
Kp =
pCO ·pH2 O
A number of models for the temperature depen-
dency of the equilibrium constant and the heat
of reaction appear in the literature. The temper-
ature dependence of the equilibrium constant is
shown in Chapter 1 (Fig. 1 and Table 3). Pres-
sure influences activity and selectivity of the CO
shift catalysts.
The various formulas, which are generally
used for calculation of K p (T) and ∆H R (T), give
only slight differences for the temperature range
of commercial processes. For the low-tempera-
ture range around 250 ◦ C, the heat of reaction
of shift conversion ∆H R is ca. − 39.6 kJ/mol, it
is about − 37.3 kJ/mol for the high-temperature
range around 500 ◦ C [139].
Above 950 – 1000 ◦ C, the water gas equilib-
rium is established rapidly enough without a cat-
alyst. In reforming processes using nickel-based
catalysts, equilibrium is still attained at much
lower temperatures. However, because nickel-
based catalysts promote methanation of carbon
oxides, they cannot be used for process steps in
which only carbon monoxide shift conversion is
desired.
The temperature ranges used in commercial
carbon monoxide shift conversions are:
a) High-temperature shift (HTS): ca. 300 ◦ C
(start of run, SOR, with new catalyst) to
510 ◦ C
b) Low-temperature shift (LTS): ca. 180 ◦ C
(SOR) to 270 ◦ C
c) Raw gas shift (RGS): ca. 200 ◦ C (SOR) to
500 ◦ C.
Some catalyst manufacturers offer a so-called
medium-temperature shift catalyst, which is nor-
mally a further stabilized LTS catalyst to operate
at temperatures up to about 320 ◦ C. Maximum
temperature for high-temperature shift (HTS) is
determined by the temperature resistance of the
catalyst (sintering); minimum temperature, by
the decrease in activity of this catalyst (large cat-
alyst volumes are required). In low-temperature
shift (LTS), the upper temperature limit is set by
accelerated recrystallization of the copper cata-
lyst (deactivation) above 270 ◦ C; the lower limit
by both the decline in catalyst activity and the
need to keep the gas inlet temperature enough
above the dew point of the gas – steam mixture
to prevent condensation of water and subsequent
damage to the catalyst. Raw gas shift (RGS)
has a wide temperature range of application and
the above explanations of temperature limits for
HTS and LTS are similarly applicable for RGS.
In practice, at start of run equilibrium con-
version can be reached whereas at end of run
conditions typically an approach to equilibrium
of about 40 ◦ C is realized.
5.1.2. Catalysts
For carbon monoxide shift conversion in so-
called clean gases (i.e., gases containing small
quantities of impurities such as sulfur or con-
densable hydrocarbons) in the high-temperature
range, iron – chromium oxide-based catalysts
with trace additions of compounds containing
sodium and potassium are used. At present
HTS catalysts are often copper promoted. In
the low-temperature range (LTS) copper – zinc
– aluminum oxide-based catalysts with traces
of potassium, etc. are commercially available
[140, 141]. Some of these added elements act
as promoters (enhancing activity, selectivity and
providing self-guarding, i.e., chemically binding
trace elements in the feed gas that would lead to
catalyst poisoning) and some as stabilizers (in-
creasing mechanical strength and active surface
compositions at elevated temperatures and pres-
sures) [142].
When new, catalysts often contain small
amounts of sulfur. At present, the catalysts are
sold mainly in tablet form and are stronger than
the broken catalysts (iron oxide) formerly in use.
In addition, their smooth surface and regular
shape result in a smaller pressure drop through
the catalyst bed.
High-temperature shift catalysts are sup-
plied in the oxidized condition (i.e., iron is
present as Fe2 O3 and chromium as Cr2 O3 ).
Generally, the reduction necessary to activate
the catalyst is not carried out before it is put into

the reactor, because the reduction process de-
creases the mechanical strength by up to 30 %.
Therefore, the catalyst is reduced in situ with
carbon monoxide- and hydrogen-laden gases,
usually the clean gas itself. To control the re-
duction rate, the reducing gas is diluted with
superheated steam or nitrogen (or both) to a
mixture containing below 5 vol % (CO + H2 ).
During reduction the temperature profile of the
catalyst bed has to be monitored carefully.
Iron oxide catalysts are resistant to apprecia-
ble amounts of impurities; even sulfur levels in
the range of 10 to > 100 ppm (mL/m3 ) can be
tolerated at the cost of activity decrease. Rapid
temperature and pressure changes caused, for
example, by water coming into contact with the
hotter catalyst (water evaporates in the pores)
must be avoided. These maloperations lead to
disintegration of the structure and, generally, to
a rapid increase in pressure drop because of the
accumulation of dust and pellet parts. All heat-
ing and cooling steps as well as pressure changes
should be carried out gradually.
Low-Temperature Shift Catalysts. Stringent
gas purity requirements must be met when us-
ing low-temperature shift catalysts because they
are very susceptible to poisoning by sulfur or
halogen compounds. Therefore, the gas must be
cleaned to sulfur and chlorine contents of < 0.1
ppm (dry) upstream of LTS conversion. If this
purity is not already met by the feed (e.g., from
steam reforming of natural gas) or achieved by
washing the raw gas (partial oxidation followed
by Rectisol wash), a “guard bed” (usually a ves-
sel filled with zinc oxide or LTS guard catalyst)
must be installed upstream of the low-tempera-
ture conversion unit.
Raw Gas Shift Catalysts. Carbon monoxide
shift conversion of gases containing apprecia-
ble amounts of sulfur or heavy hydrocarbons
such as tar is known as raw gas shift conver-
sion. For such gases catalysts consisting mainly
of cobalt and molybdenum are used instead of
the iron – chromium type. The activity of cobalt
– molybdenum-based catalysts increases signif-
icantly between 4.0 and 8.0 MPa, whereas with
HTS iron oxide catalysts, increasing the operat-
ing pressure above 4.0 MPa has practically no
effect on the volume of catalyst required. RGS
catalysts attain their full activity only in the sul-
fided condition. Therefore, they must be presul-
fided before installation or sulfided during start-
Gas Production 79
up. A minimum content of sulfur compounds in
the dry raw gas of ca. 100 to 1500 ppm (for gases
from partial oxidation; the value depends on the
steam: sulfur ratio) is required in normal opera-
tion to maintain catalyst activity. The minimum
sulfur content in the feed gas also depends on
other operating conditions (e.g., temperature).
The sulfur content has no upper limit. The RGS
offers the advantage of allowing sulfur and car-
bon dioxide removal to be accomplished in one
step downstream the RGS unit [140].
The volume of catalyst required depends
on the partial pressures of reacting compo-
nents, the desired carbon monoxide content of
the converted gas, and the reaction tempera-
ture. Normally, operating parameters are chosen
to achieve space velocities of 1000 – 3000 m3
(STP) of gas per cubic meter of catalyst per hour
in the HTS range and 2000 – 5000 m3 (STP) per
cubic meter of catalyst per hour in the RGS and
LTS range. If necessary, the process is divided
into several steps with intermediate cooling or
water quenching (see Section 5.1.5).
5.1.3. Clean Gas Shift Conversion
If the carbon monoxide-containing gas is sub-
stantially free of sulfur and heavy hydrocarbons,
clean gas shift conversion is applied. In case the
gas had to be desulfurized in an upstream purifi-
cation stage, a cooler – saturator system is fa-
vorable. For naturally clean gases, (e.g., steam
reformer outlet gas) only a simple HTS reactor
is necessary.
Desulfurized feed gases derived from up-
stream partial oxidation and a physical or chem-
ical washing unit usually enter the CO shift unit
at a temperature between 20 and 120 ◦ C. Thus,
even if they are saturated with water vapor, the
addition of a considerable quantity of high-pres-
sure steam is required to effect satisfactory car-
bon monoxide shift conversion. For example,
to lower the carbon monoxide content of a gas
available at ca. 5.4 MPa and ambient tempera-
ture from 45 vol % (dry) to a residual ca. 3 vol %
(dry) in two stages at a final reaction tempera-
ture of 380 ◦ C, the addition of 1.18 kg of exter-
nal HP-steam per cubic meter (STP) of gas is
necessary. The cooler – saturator system, which
generates steam in the saturator by using the re-
action heat of the carbon monoxide shift con-
80 Gas Production
version, enables the quantity of external process
steam to be lowered to 0.33 kg/m3 (STP) of gas.
Cooler – Saturator System. Shift feed gas
enters the saturator (a) at ambient temperature
and rises through the tower packing while be-
ing sprayed with hot water (see Fig. 34). The
gas becomes saturated with steam at ca. 225 ◦ C.
Heating of the gas – steam mixture is continued,
more steam (0.33 kg/m3 (STP) dry gas) is added,
and the resulting mixture is fed to the first reac-
tion zone (c). The temperature of the mixture
rises due to the heat of reaction to about 500 ◦ C.
The first converter outlet CO concentration is
about 6 to 8 vol % (dry). The hot gas is fed first to
a gas – gas heat exchanger (b) to preheat the in-
coming mixture and then into a gas – water heat
exchanger (e) to heat circulating water; by this
means, it is cooled to ca. 350 – 360 ◦ C. At this
temperature, it enters the second reaction zone
(d), where carbon monoxide is converted further
to a residual content of ca. 3 vol % (dry), the gas
being simultaneously heated to ca. 380 ◦ C.
Figure 34. Flowsheet of a two-stage CO conversion plant
with cooler – saturator system
a) Saturator; b) Gas – gas heat exchanger; c) Reactor 1;
d) Reactor 2; e) Gas – water heat exchanger; f) Cooler;
g) Waste Heat Recovery
Converted gas leaving the second reaction
zone is cooled in a second gas – water heat ex-
changer (e). Then it enters the cooler (f) at ca.
230 ◦ C. Here it is irrigated with colder water
while it flows upward through a packed bed. By
this means, most of the steam condenses, and
water leaving the cooler is heated approximately
to the dew point of the converted gas. The wa-
ter leaves the cooler at ca. 210 ◦ C. The cooler
is often divided into two sections: the bottom
section is fed directly with most of the water
leaving the saturator; the top section is fed with
a side stream that has been cooled to ca. 50 ◦ C.
The heat thus removed is used e.g., for boiler
feedwater preheating, demineralized water pre-
heating, etc. (g). By using such an arrangement,
the gas can be cooled to about 60 ◦ C.
Water from the cooler is heated to ca. 250 ◦ C
in the two gas – water heat exchangers (e) be-
fore entering the saturator (a), which it leaves at
ca. 160 ◦ C. Alternatively to the shown arrange-
ment, in larger plants, the first gas – gas heat ex-
changer (b) can be installed inside reactor 1, to
avoid the hot transfer piping.
Countercurrent Cooling Reactor. In smaller
plants, a countercurrent cooling reactor (Fig. 35)
is often used instead of two reaction steps in
series. Whereas the reaction in a simple fixed-
bed reactor proceeds adiabatically, which neces-
sitates the two-stage mode of operation, a much
more favorable temperature profile is achieved
in the countercurrent cooling reactor.
Figure 35. Countercurrent cooling reactor
a) Gas entry into the cooling tubes; b) Surface of catalyst
bed; c) Catalyst support grid; d) Manhole
The gas – steam mixture, which is not pre-
heated to catalyst inlet temperature, enters the
annular space between reactor shell and cata-
lyst vessel, flows downward through this space,
and enters the tubes of the catalyst vessel.
While flowing through these tubes which are
surrounded with catalyst, the mixture is heated

to ca. 380 ◦ C. It then enters the catalyst bed
from above. Due to the interaction between the
temperature rise caused by the heat of reaction
and the cooling effect of the gas mixture flow-
ing through the cooling tubes, the temperature
curve illustrated in Figure 36 develops. This type
of reactor combines a high reaction rate at high
temperature in the top section with a favorable
equilibrium in the bottom section.
Figure 36. Temperature profile in countercurrent cooling
reactor
a) Gas entry into cooling tubes; b) Gas entry into catalyst;
c) Gas outlet (denotations a to c correspond with Fig. 35)
Carbon Monoxide Shift Conversion of
Steam Reformer Outlet Gas. Shift conversion
can be carried out more easily on product gases
of a steam reformer for the following reasons:
(1) the content of carbon monoxide is far lower
(ca. 12 – 15 vol % in dry gas) compared to syn-
gas produced by partial oxidation or coal gasi-
fication; that means generation of less reaction
heat in CO conversion; (2) the required steam is
already present in the steam reformer outlet gas,
i.e., the gas has only to be cooled in the down-
stream waste-heat boiler to the inlet temperature
of the shift converter (ca. 300 – 350 ◦ C); (3) the
gas is essentially free of catalyst poisons, as the
reformer feed has to be purified before, because
of the sensitivity of the reformer catalyst.
An example is the production of synthesis
gas for ammonia manufacture from natural gas.
After reforming in the primary and secondary re-
Gas Production 81
former, and initial cooling in a waste-heat boiler,
the reformed gas is, e.g., available at 2.9 MPa
and 350 ◦ C, and a steam content of 0.64 kg/m3
(STP). It contains 10.5 vol % (dry) carbon diox-
ide, 11.7 vol % (dry) carbon monoxide, and 55.5
vol % (dry) hydrogen, the remainder being nitro-
gen and methane. After passing through the HTS
conversion step, a carbon monoxide content of
2.2 vol % (dry) is obtained at 405 ◦ C. The gas,
which still contains 0.52 kg of steam per cubic
meter (STP), is cooled to 220 ◦ C and then fed to
the LTS step. There the carbon monoxide con-
tent is decreased to ca. 0.3 vol % (dry), while the
temperature increases to 232 ◦ C.
Shift conversion of these gases is carried out
either in one step in a HTS converter or in two
steps, with intermediate cooling, in HTS and
LTS converters. More recently quasi isothermal
LTS reactors have been installed, reaching low
CO contents at their outlet in a single step [143].
As a byproduct a significant amount of methanol
is normally produced [141, 144].
5.1.4. Raw Gas Conversion
Raw gas conversion (sometimes also termed
“sulfided CO shift”) denotes the conversion of
gases containing significant quantities of sulfur,
soot, or condensable hydrocarbons. There are
two principal industrial applications: (1) shift
conversion of gases from heavy-oil gasification
that have not been cooled and desulfurized but
have only undergone hot quenching to add the re-
quired steam and remove soot; and (2) shift con-
version of the carbon monoxide in gases from
coal pressure gasification that contain not only
sulfur but also saturated and unsaturated hydro-
carbons, including tars. Cobalt – molybdenum
based catalysts have proved particularly effec-
tive for converting both types of gas.
The carbon monoxide content (ca. 45 vol %,
dry) of a gas from partial oxidation of heavy
oil enters the carbon monoxide shift reactor at
about 250 ◦ C with a steam: dry gas volume ra-
tio of ca. 2.4. The carbon monoxide content can
be reduced to ca. 1.6 vol % (dry) over a cobalt
– molybdenum based catalyst. Residual carbon
monoxide contents of 0.5 – 1.0 vol % (dry) are
attainable in a two-stage system even at lower
steam: dry gas ratios. The sensible heat of the
product gas is used to generate steam and to
82 Gas Production
preheat feedwater. Impurities in the gases for
raw gas conversion, especially formic acid ne-
cessitate the use of mostly austenitic materials
for streams with temperatures below the wa-
ter dew point. Carrying out shift conversion on
raw gases produced by coal pressure gasifica-
tion is a good way of “detoxifying” town gas.
The amount of steam present in the gas at 3.0
MPa and 180 ◦ C, ca. 0.6 kg/m3 (STP), is suf-
ficient to reduce the carbon monoxide content
from, e.g., 15.5 to ca. 5.0 vol % (dry). The cobalt
– molybdenum based catalyst has a very useful
side effect: unsaturated hydrocarbons in the gas
are hydrogenated almost completely. Parallel to
the CO shift conversion reaction COS is con-
verted to H2 S; i.e., COS contents in the shifted
gas reach low values close to equilibrium at cat-
alyst outlet conditions.
5.1.5. General Comments on Reactor
Arrangements
Apart from one-reactor applications several two-
reactor systems are of commercial interest: two
HTS (or RGS) reactors in series or one HTS
followed by one LTS reactor, in each case with
intermediate cooling. In the latter case a “guard
bed” filled with zinc oxide is often installed bet-
ween the HTS and LTS reactors to ensure that
gas entering the LTS step is largely sulfur and
halogen-free. Alternatively, the “guard bed” is
filled with a smaller amount of LTS guard cata-
lyst. Some HTS processes include water quench-
ing between two reactor beds to cool the gas on
the one hand and to add steam as a reactant on
the other hand. In these concepts special caution
has to be taken to avoid wetting of the catalyst.
5.1.6. Noncatalytic Quench Conversion
A less frequently used method of carbon monox-
ide shift conversion on raw gases is noncatalytic
quench conversion. Here, advantage is taken of
the fact that the water gas equilibrium is attained
fairly rapidly above ca. 950 ◦ C, even without
catalysts. If, for example, oxo synthesis gas with
a hydrogen: carbon monoxide volume ratio of
1.25 is to be produced from raw gas obtained by
partial oxidation of asphalt and containing 48.9
vol % (dry) carbon monoxide and 43.9 vol %
(dry) hydrogen, then 0.4 kg of cold water per
kilogram of asphalt is sprayed into the hot (ca.
1570 ◦ C) gas. As a result of cooling caused by
the heating and evaporation of water and the as-
sociated carbon monoxide shift conversion (heat
of reaction), the water gas equilibrium is attained
at 1250 ◦ C. The carbon monoxide content is then
38.3 vol % (dry) and the hydrogen content 47.8
vol % (dry), with a H2 : CO ratio as desired.
5.2. Carbonyl Sulfide Conversion
In all gasification processes based on sulfur-con-
taining feedstocks, carbonyl sulfide is produced
as well as hydrogen sulfide. For example, by par-
tial oxidation of vacuum residues with a sulfur
content of 3 wt %, a raw gas containing 0.71
vol % (dry) of hydrogen sulfide and 0.03 vol %
(dry) of carbonyl sulfide is formed. Many mod-
ern gas washing processes remove carbonyl sul-
fide together with hydrogen sulfide. A selective
carbonyl sulfide conversion (i.e., without par-
allel carbon monoxide conversion in a HTS or
RGS converter, see Section 5.1) is limited to ap-
plications where there is no need for deep desul-
furization (e.g., fuel gas for gas turbines).
Conversion of organic sulfur compounds in
feedstocks for tubular reforming by hydrogen-
ation over cobalt – molybdenum and nickel –
molybdenum catalysts is described in Section
2.2.2.
Hydrogenation of carbonyl sulfide over iron
oxide and cobalt – molybdenum based (see Sec-
tion 5.1) catalysts occurs simultaneously with
carbon monoxide shift conversion, and equilib-
rium in the form
0
H2 +COS
H2 S+CO ∆HR = +10.9 kJ/mol
being established. In the CO shift conversion
range at high temperatures of 350 – 500 ◦ C, the
equilibrium and the kinetics of this reaction lead
to high COS conversion rates. When the gas
mentioned above undergoes carbon monoxide
shift conversion, the concentration of carbonyl
sulfide in the product gas typically reaches val-
ues below 10 ppm (dry). (Table 3 lists a number
of values of the equilibrium constant for this re-
action in relation to temperature.)
A selective transformation of carbonyl sul-
fide to hydrogen sulfide is required in gases in
which carbon monoxide shift conversion is not

desired. Catalysts have been developed for the
selective conversion of carbonyl sulfide to hy-
drogen sulfide which are inactive for the wa-
ter gas shift reaction. These catalysts promote
hydrolysis of carbonyl sulfide according to
0 oxides in hydrogen production: upstream of
COS+H2 O
H2 S+CO2 ∆HR = −30.2 kJ/mol
This reaction is catalyzed by chromium
– aluminum oxide-based promoted catalysts,
which work in a sulfided state. The commer-
cially available catalysts are mainly not subject
to poisoning by heavy metals and arsenic; but
halogen compounds will lead to reduction of ac-
tivity, selectivity, and lifetime. These catalysts
are used at 150 – 320 ◦ C; satisfactory equilib-
rium is attained at space velocities between 500
and 2000 m3 (STP) per cubic meter of cata-
lyst per hour [145]. As at lower temperatures
the equilibrium conditions favor COS hydroly-
sis, less steam in the feed gas is needed to reach
desired hydrolysis rates. (Values for equilibrium
constants as a function of temperature are shown
in Table 3.)
A typical reduction of the carbonyl sulfide
content in gases from partial oxidation [assumed
gas compounds (dry): 45 vol % H2 , 45 vol %
CO, 5 vol % CO2 , 0.71 vol % H2 S, 300 ppm
(mL/m3 ) COS] to about 10 ppm is achievable
by COS hydrolysis at 170 ◦ C. A steam content
of 0.086 kg per cubic meter (STP) of gas in this
example corresponds to a saturation tempera-
ture of 150 ◦ C at 5.0 MPa. In parallel to COS
hydrolysis the contents of CS2 and HCN are
also significantly reduced. For some applica-
tions a separate bed for hydrogenation/hydro-
lysis of these compounds has to be installed ad-
ditionally. For gases with low total sulfur con-
tent there are zinc oxide-based “absorption cat-
alysts” commercially available, which can hy-
drolyze COS in the presence of steam (low con-
centrations) before H2 S is absorbed in the same
bed.
5.3. Methanation and Methane
Synthesis
5.3.1. Definitions and Applications
Methanation is generally defined as the cat-
alytic reaction of hydrogen with carbon monox-
ide and/or carbon dioxide, forming methane and
Gas Production 83
water, according to the description given in Sec-
tion 5.3.2. Two main applications of methana-
tion exist, which require very different technical
solutions:
1) Methanation for the elimination of carbon
this final purification step the concentrations
of harmful carbon oxides are rather low and
the exothermic methanation reaction there-
fore causes only a moderate temperature in-
crease, i.e., a single methanation step is suffi-
cient (see Section 5.3.3).
2) Methanation for the production of SNG (Sub-
stitute Natural Gas): in this application, also
called methane synthesis, hydrogen shall be
converted to methane as completely as possi-
ble. Due to the strongly exothermic reaction
and the high concentrations of all reactants
measures have to be taken to limit temper-
ature rises. As also the thermodynamics, i.e.,
the relevant equilibrium, ask for relatively low
temperatures to yield high methane and cor-
respondingly low hydrogen contents in the
product, usually multiple-stage reaction sys-
tems will be required (see Sections 5.3.4 and
5.3.5).
Application (1) must be regarded as a well
established technique with little incentive to im-
provements. It is widely used in hydrogen pro-
duction, although nowadays pressure-swing ad-
sorption (PSA) systems for hydrogen purifica-
tion dominate the market. Catalytic systems may
be damaged by too high temperatures due to
breakthrough of carbon oxides as a result of sud-
den malfunctions of the upstream purification
systems.
Application (2), the production of SNG, has
lost commercial interest at present due to the
increased availability of natural gas. The price
of SNG cannot compete with that of natural gas.
The development of new techniques for this kind
of plants has therefore been terminated.
SNG production plants have demonstrated
the reliability of processes for conversion of
naphtha to SNG (Baltimore, USA) or coal to
SNG (North Dakota, USA). Special local con-
ditions — such as isolated distribution systems
or missing storage capabilities — may be the
reason for temporary implementation of SNG
plants (for instance in West-Berlin before the
German reunification, where only naphtha could
84 Gas Production
Table 26. Equilibrium constants and heats of reaction (according
be stored at the time). A methanation system to [147] for
at low temperatures (with ruthenium-based cat-
alysts instead of normally applied nickel cata-
lysts) may find application in space technology
[146]. In this projected application carbon diox-
ide from the breathing air is methanated in com-
bination with a water electrolysis, thereby re-
gaining oxygen for the biological cycle.

5.3.2. Principles of Methanation

The principle of catalytic synthetic production

of methane from carbon monoxide and hydro-
gen was discovered in 1902 by Sabatier and
Senderens. It is described by

CO+3 H2
CH4 +H2 O

Carbon dioxide can also be converted to In the purification of synthesis gas with a
methane according to large excess of hydrogen, the reaction rate law
CO2 +4 H2
CH4 +2 H2 O
is simplified to

Both reactions are linked by shift conversion, rCO = k2 ·pm

CO

which is always observed simultaneously when-
ever active catalysts are used:
CO+H2 O
CO2 +H2
Many observations indicate that the transfor-
mation of carbon dioxide to methane is initiated
by a reverse shift conversion reaction with hy-
drogen to yield carbon monoxide and steam. The
carbon monoxide formed then reacts to yield
methane:
Summaries and details can be found in the liter-
ature; see [148 – 150].
Kinetics must also be considered when inves-
tigating the possibility of undesirable side reac-
tions. Kinetic effects have to be used to avoid
the formation of carbon, because methanation
usually begins in the temperature region where
suitable thermodynamic conditions prevail for
the Boudouard reaction to occur:
2 CO
C+CO2

(see Section 1.3). If thermodynamic equilib-

Both reactions for the formation of methane
are strongly exothermic, as shown by Table 26.
This table also indicates that low temperature
and high pressure are required or favorable for
high methane yield.
Kinetics. The mechanism and kinetics of
methanation have been investigated, but these
studies do not yield uniform results. The rate
of conversion of carbon monoxide is often de-
scribed formally by
rCO = k1 ·pm n
CO ·pH2
rium calculations indicate a possible buildup of
carbon in the outlet region of the reactor, this un-
desirable side reaction cannot be excluded and
may call for changes in process conditions. At
the outlet zone of methanation reactors, attention
must also be paid to the methane decomposition
reaction
CH4
C+2 H2
(see also Section 1.3.). However, a small
residual hydrogen content and moderate temper-
ature normally prevent this reverse reaction.

with m = 0.7 – 1.0 and n = 0.3 – 0.5.

 Gas Production 85

Catalysts. For the removal of carbon oxides
from synthesis gases, catalysts with usually <
15 wt % nickel are used predominantly. Acti-
vated alumina, magnesium oxide and mixtures
thereof are widely used as carrier materials. For
the synthesis of methane from gases rich in car-
bon monoxide, catalysts with a high nickel con-
tent, similar to those used in reforming naph-
tha to a methane-rich gas, are usually employed.
Catalyst poisons, must be eliminated carefully to
the same level as in naphtha reforming (see Sec-
tion 2.4.4) or even lower, because deactivation
with time depends primarily on such impurities
in the synthesis gas. Catalysts of the naphtha
reforming type usually reach their limit of op-
eration at about 500 ◦ C. High-nickel catalysts
with special aluminum oxide carriers and stabi-
lization by zirconium oxide, which are capable
of operating at 300 – 700 ◦ C, are also available.
The catalysts are used preferably in the form
of cylindrical tablets measuring 5 × 5 or 8 × 8
mm.
Catalysts based on ruthenium have been tried
repeatedly for methanation but have not found
the broad application of nickel-based catalysts.
Raney nickel coated reaction tube systems are
also of little interest, because replacement of the
spent catalyst appears complicated.
Metal Carbonyl Formation. Precaution must
be taken with nickel-containing catalysts to pre-
vent formation of highly poisonous nickel car-
bonyl [Ni(CO)4 ] (TLV 0.1 ppm (mL/m3 ) or 0.7
mg/m3 ; see [151]).
In particular, low temperatures must be
avoided because they favor the formation of car-
bonyls, as shown by Table 27. Generation of car-
bonyls is favored by nickel in reduced form, high
total pressure, or high partial pressure of carbon
monoxide [152]. The reaction is also promoted
by sulfur, selenium, and tellurium. In practical
operation of methanation plants, temperatures ≤
200 ◦ C at the nickel catalyst must be avoided,
and procedures for start-up and shutdown must
be adjusted accordingly. Formation of iron car-
bonyl also has to be prevented because of its
toxicity and general corrosion problems, and be-
cause iron carbonyl decomposes and forms iron
layers on the active surface of the catalyst as the
temperature increases. Thus, carbon monoxide-
laden synthesis gases must be heated in stain-
less steel heat exchangers. Many years of plant
operation have shown that with adequate pre-
cautions, the formation of carbonyls can be sup-
pressed successfully.
Table 27. Calculated nickel carbonyl content at equilibrium for
various carbon monoxide concentrations as a function of
temperature for a total pressure of 1.48 MPa (according to [152]),
ppm (mL/m3 )
Temperature, CO content, mol%
◦
C 0.2 0.5 1.0 2.0 3.2
66 0.3 12 190 3 000 20 000
93 0 0.2 3 49 320
121 0 0 0.1 1.6 11
149 0 0 0 0.1 0.5
177 0 0 0 0 0.03
204 0 0 0 0 0
5.3.3. Methanation as a Step in Hydrogen
Purification
Carbon oxides are often poisonous to catalytic
hydrogenation processes. Their simultaneous
elimination is possible by means of a metha-
nation process step, which has been used widely
since the 1950s and is nowadays competing with
pressure-swing adsorption processes. Methana-
tion remains the normal purification method for
ammonia synthesis gas production, especially
by secondary air reforming. Here, the nitrogen
content prevents the use of other methods.
As shown in Figure 37, the inlet gas, con-
taining ca. 0.5 – 0.8 mol % of carbon monoxide
and the same amount of carbon dioxide, is heated
by methanated gas in a heat exchanger (b). The
final inlet temperature to the adiabatic reactor —
typically 300 – 330 ◦ C — may be achieved by a
fired trim heater (c). In the adiabatic shaft reactor
(a) filled with nickel catalyst, carbon monoxide
and carbon dioxide are converted with hydrogen
to methane and water vapor. Because the tem-
perature increase in the reactor is ca. 70 K for
each percent of carbon monoxide and about 55 K
for each percent of carbon dioxide, the result-
ing outlet temperature can reach ca. 400 ◦ C and
the temperature gradient is then large enough to
shut off the trim heater in continuous operation.
Instead of the fired trim heater, other arrange-
ments of heat exchangers in combination with
the reforming plant are possible, as well as elec-
trically operated start heaters. Purified hydrogen
is then cooled to ambient temperature in the heat
exchanger (b) and a final cooler (d), which also
condenses most of the vapor formed.
86 Gas Production
Figure 37. Methanation as a purification step for hydrogen
or synthesis gas
a) Reactor; b) Heat exchanger; c) Fired trim heater;
d) Cooler
In synthesis gas purification of this type, the
total content of carbon oxides is limited to ca. 2
vol %; otherwise, the temperature limits of the
catalyst would be exceeded and the final content
of methane in the hydrogen would be too high.
Because of the loss of hydrogen by methanation,
carbon oxides contents no greater than 0.8 % to-
tal are aimed at. Additionally, the residual con-
tent of carbon oxides is increased by higher out-
let temperature and thus will not remain below
the accepted tolerance of ca. 10 ppm (mL/m3 )
for the sum of carbon monoxide and carbon
dioxide.
5.3.4. Methanation of Rich Gas
Although methanation as a method of purifying
synthesis gas yields only small absolute quan-
tities of methane, methanation of rich gas and
methane synthesis from gases high in carbon
monoxide (e.g., produced by coal gasification)
intentionally generate methane as product. Pro-
duction of SNG by gasification of coal is be-
ing considered as a long-term replacement for
gaseous hydrocarbons of natural origin when the
latter are no longer available in sufficient quan-
tity. In contrast, production of methane from rich
gas (see Section 2.4.4) is restricted to specific
areas where naphtha is abundant but no natural
gas is available.
When SNG is produced from naphtha, the
methane content of the rich gas is typically ca.
70 vol % (see Fig. 10, Section 2.4.4), whereas
hydrogen amounts to ca. 7 % and carbon diox-
ide 25 %. Less than 0.5 % carbon monoxide is
present, and unreacted steam from naphtha gasi-
fication amounts to ca. 1.30 mol of H2 O per
mole of dry gas. Such a gas mixture can be en-
riched further by admitting it at an inlet temper-
ature around 300 ◦ C (i.e., after cooling down-
stream of gasification) to an adiabatic shaft reac-
tor containing a nickel catalyst identical or sim-
ilar to that used in naphtha reforming. Because
the portion of unreacted steam is quite high and
further steam is formed during the reaction, the
degree of methane formation is limited in this
so-called wet methanation step.
After cooling of the gas and condensation of
steam, the methane content can be increased fur-
ther by another methanation step (dry methana-
tion), which may be up- or downstream of the
required carbon dioxide removal. The upstream
arrangement yields better methane quality, but
the danger of carbon formation is higher due to
the thermodynamic possibility of a reverse shift
reaction and consequent formation of carbon ac-
cording to the Boudouard reaction. Installation
of the dry methanation step downstream of the
carbon dioxide scrubbing system allows milder
reaction conditions, but the carbon dioxide and
hydrogen content of the product is increased
slightly because of the need to provide excess
carbon dioxide for the reaction of hydrogen.
A typical analysis of the final SNG is: meth-
ane 98.5 vol %, carbon dioxide 0.5 vol %, hy-
drogen 1.0 vol % and carbon monoxide < 0.1
vol %.
Figure 12, Section 2.4.4, shows a one-stage
methanation system for rich gas installed up-
stream of the CO2 removal system as part of the
total plant concept for the production of SNG
from naphtha.
5.3.5. Methane Synthesis from Gases with
High Carbon Monoxide Content
Synthesis gases high in carbon monoxide are
generated by various coal and oil gasification
processes. These processes naturally result in
different qualities of synthesis gas according to
the feedstock used, the upgrading processes for

synthesis gas preparation, and the gasification
process itself. Whereas high-temperature gasi-
fication processes yield high concentrations of
carbon monoxide and little methane, interest in
SNG production is concentrated on gasification
processes that yield high methane content in the
raw gas. This is possible, for instance, with Lurgi
pressure gasification of coal, especially when
gasification pressures of 8.0 – 10.0 MPa are ap-
plied, which has been successfully tested (see
Section 4.4). Methanation processes with little
methane in the raw gas suffer principally from
(1) high exothermic heat release during metha-
nation, (2) the very large quantities of synthe-
sis gas that must be handled (four to five vol-
umes of dry synthesis gas yield one volume of
methane), and (3) the high proportion of steam
formed during methane synthesis, which lim-
its the directly achievable SNG quality in wet
methanation steps.
Synthesis gases for methane synthesis are
often classified by their stoichiometric number
(SN), i.e., the ratio of the reactable hydrogen
volume to the pro rata volume of carbon oxides:
η·vH2
SN =
3vCO +4vCO2
where η stands for an equivalent hydrogen con-
sumption required for the hydrogenation of un-
saturated and higher hydrocarbons in producing
methane.
Because SNG specifications demand a hydro-
gen content of <10 vol %, a general classifica-
tion may be SN ≤ 1.05. Because of restrictions
in carbon dioxide content as well, the synthesis
gas must meet the condition 0.98 < SN < 1.03
for stoichiometric methane synthesis, which is
suitable for direct production of SNG. Such stoi-
chiometric methane synthesis allows synthesis
gas to be prepared by shift conversion and carbon
dioxide removal. After methane synthesis, only
compression to pipeline pressure (if the gasi-
fication pressure is not high enough) and dry-
ing (e.g., by a glycol system) are necessary. The
quality of SNG varies slightly because fluctua-
tions of the stoichiometric number are inevitably
caused by variables and control functions of the
gasification and upgrading processes.
In stoichiometric methane synthesis, little
risk exists of carbon formation according to the
Boudouard reaction, even in high-temperature
methanation up to 700 ◦ C. These problems be-
come more serious at lower SN numbers. Lower
Gas Production 87
stoichiometric numbers always require carbon
dioxide removal as the final step before drying.
The allowable load of carbon monoxide for the
stoichiometric number of the synthesis gas must
be determined experimentally for each gasifica-
tion process. Individual optimization is neces-
sary to attain lowest product costs, because shift
conversion may be expensive if the necessary va-
por is not provided with the raw gas. Among a
vast variety of process configurations developed
in the 1970s, the following are reportedly avail-
able for commercial operation. However, only
the process with recycle has demonstrated relia-
bility under the harsh conditions of commercial
production, due to the lack of interest in SNG.
Besides the stoichiometric number, the
highly exothermic reaction generally creates a
problem for the design of methane synthesis
plants: either the temperature increase must be
limited by recycling of reacted gas or steam dilu-
tion, or special techniques such as isothermal re-
actors or fluidized beds, each with indirect cool-
ing by evaporating water, must be used.
Recycle Methane Synthesis. Figure 38
shows a schematic of a methane synthesis
plant with hot recycle. The type shown is de-
signed as a two-stage recycle system with a fi-
nal countercurrent-cooled reactor. These plants
were originally designed for a recycle quantity
such that 500 ◦ C is not exceeded at the outlet
of the adiabatic reactors. Current systems, op-
timized with regard to low secondary energy
requirements, are available for maximum tem-
peratures up to 650 ◦ C. Inlet temperatures are
ca. 300 ◦ C, which is also the operating range
of the recycle compressor. An advantage of
the hot recycle is that water vapor formed dur-
ing the methanation reaction is not condensed
and, therefore, the stoichiometric number is
not changed for the stages processing feed gas.
Recycle systems show a high flexibility for ac-
cepting synthesis gases of very different natures
[153, 154]. The waste-heat recovery system is
normally designed to generate saturated steam
up to 10.0 MPa, but superheated steam may also
be withdrawn. Replacing the recycle compres-
sor by a gas ejector reportedly produces positive
results [155].
The higher the temperature selected for the
first stage of methane synthesis, the more stages
88 Gas Production
Figure 38. Recycle methane synthesis
a) Recycle reactors; b) Steam drum; c) Countercurrent cooling reactor; d) Air-cooled cooler; e) Hot recycle compressor
must be applied to reach specification-grade
SNG, for thermodynamic reasons. Therefore,
with high-temperature methanation in the recy-
cle stage(s), an intermediate step without feed
gas addition at ca. 300 – 460 ◦ C is required up-
stream of a final dry or wet methanation stage.
The countercurrent cooling reactor in Figure 38,
has a similar design to that described in Section
5.1.3 (Fig. 35). It allows product quality to be
reached in one final wet step; otherwise, more
stages are required to achieve the same analysis.
Steam Quenching Methane Synthesis. For
synthesis gases with low stoichiometric num-
bers (low H2 : CO ratio), steam must always be
added to prevent carbon formation. For optimum
results, the required quantity of steam is mixed
with a proportion of the feed gas in such a way
that the temperature increase in the first metha-
nation stage is kept within allowable limits and,
after heat removal, a further portion of the feed
gas is admitted to the first intermediate product
gas stream as quenching stream. The quenching
procedure after cooling is repeated until all the
feed gas is consumed. Thus, a multistage con-
cept results, depending on the inlet gas compo-
sition, as shown in Figure 39 for the RM pro-
cess [156]. With the addition of steam, the equi-
librium composition of any intermediate prod-
uct gas is not favorable enough to enable direct
production of specification-grade SNG in a wet
methanation step. The removal of carbon diox-
ide, therefore, is followed by a final, dry metha-
nation stage.
Fluidized-Bed Methanation. Intensive re-
search and demonstration have been reported
for the methanation of feed gases of unfavorable
composition, with little or no addition of steam,
in a cooled fluidized-bed reactor in one step
without an additional cleanup reaction (Com-
flux process) [157]. The dangers of carbon for-
mation, catalyst deactivation by high carbon
monoxide partial pressure, and excessive cata-
lyst consumption by the fluidized-bed process
are said to have been overcome, and operation
up to 6.0 MPa has been demonstrated success-
fully in the pilot plant.

Figure 39. Flow principle of multi stage quenching system – RM process
Isothermal Operation. By increasing the
allowable temperatures for methanation cata-
lysts, methane synthesis can be performed by a
once-through method in quasi-isothermal reac-
tors cooled by evaporating water, generating sat-
urated steam. Under favorable conditions, such
systems produce specification-grade SNG in
only one catalytic step (IRMA process), but su-
perheated steam can be produced only by com-
bining isothermal and adiabatic reactors [158].
Any traces of sulfur compounds must be elim-
inated carefully, because poisoning of the cata-
lyst will displace the temperature profile in the
reactor and the reaction will not go to com-
pletion as the catalyst lifetime expires. Tests
with isothermal reactors have been performed
for methane synthesis within the ADAM – EVA
systems for energy transport [159].
The ADAM – EVA Concept (Long-Distance
Energy Transport System). Generally, methane
synthesis is used to generate methane, the heat
of reaction being an inevitable byproduct. How-
ever, a proposal by the Jülich Nuclear Re-
search Center (KFA-Jülich, Germany) and the
Rheinische Braunkohlenwerke (Cologne, Ger-
many) uses the energy release of the methana-
tion reaction as the essential product. The energy
demand for the steam reforming of methane is
provided by a nuclear high-temperature reactor;
the resulting synthesis gas is then retransformed
into methane a few hundred kilometers away,
thereby providing thermal energy up to 650 ◦ C.
The methane is routed back to the nuclear system
by a second pipeline to restart the cycle; thus, no
fossil energy is used up.
Gas Production 89
CH4 +H2 O
CO+3 H2
Endothermic Exothermic
By the combination of power generation and
energy distribution at a level of ca. 150 ◦ C, an
overall efficiency of about 60 % can be reached
for such a chemical heat pipe system. A gen-
eral flow diagram of this process is given in
[160]. The use of high-temperature solar heat-
ing instead of nuclear power has been proposed
for steam reforming of methane, however, so-
lar ADAM – EVA systems may be restricted to
a few favorable locations. Plans have been re-
ported to provide energy that has been recovered
and converted by high-temperature reforming in
the Negev Desert to the industrial zones of Israel.
Studies have been made on the replacement
of steam in the reforming step by carbon dioxide
as oxidant [161]:
CH4 +CO2 →2 CO+2 H2
Although this reaction sequence significantly
reduces the load in steam generation and can im-
prove overall efficiency, transport of the thermo-
dynamically necessary excess carbon dioxide in
pipelines for both directions reduces this advan-
tage. In addition, the danger of carbon formation
in both reforming and methane synthesis at rela-
tively high pressure must be examined carefully.
Other Synthesis Processes.
Methanation of Raw Gases. The dry product
gas volume from methanation is only 20 – 35 %
of the synthesis gas volume, depending on the
gasification process and its yield of primary
methane. Because nickel catalysts require com-
plete removal of poisonous sulfur compounds,
90 Gas Production
relatively large amounts of gas must be handled
in the upstream treating units. The Gas Research
Institute in Chicago has proposed direct metha-
nation of raw gases containing sulfur and car-
bon dioxide on special catalysts, to reduce gas
volumes in acid gas removal. Savings in over-
all steam balance and in capital investment are
claimed for such process routes. A final metha-
nation step for cleanup in a sulfur-free atmo-
sphere yields specification-grade SNG.
Liquid-Phase Methanation. A proposal by
Chem Systems, Hackensack, N.J., is based on
conventional gas preparation with methanation
in the liquid phase [162]. Similar to processes
employing fluidized-bed methanation or isother-
mal reactors, liquid-phase methanation appears
to be able to handle high carbon monoxide con-
centrations and to yield high-quality methane
in a single reactor. An inert liquid (aliphatic
oil) containing dispersed catalyst is circulated
and the feed gas is passed through this. The
exothermic reaction heat is taken up by the liq-
uid, mainly as sensible heat and partly by vapor-
ization, resulting in excellent temperature con-
trol.
5.4. Absorption Processes
5.4.1. General
Principles. Processes that use a liquid sol-
vent to remove one or more compounds from a
gas stream are called absorption processes [140,
163 – 165] (→ Absorption).
The main purpose of absorption processes in
gas production is the removal of acid gas com-
ponents. They can also be used successfully to
purify gases containing low concentrations of
other components such as ammonia, higher hy-
drocarbons, water, cyanide, and organic sulfur
compounds. Absorption processes are further
applied to the withdrawal of gas constituents
poisonous to catalysts or to the environment and
also for the recovery of liquid gas or gasoline
components from refinery gases.
In electric power generation from coal or liq-
uid hydrocarbons by the combined power cycle
process (see Section 7.3), absorption is used to
selectively remove sulfur compounds and other
impurities such as cyanide and mercury from the
gas in order to meet gas turbine requirements
and environmental regulations. So-called zero-
emission IGCCs are discussed in view of CO2
emissions regulations and greenhouse gas abate-
ment. Carbon of the feedstock is converted to
carbon dioxide, which is removed in the absorp-
tion process and must be concentrated in a pure
carbon dioxide stream for sequestration (see Fig.
59).
In the absorber, gas and liquid are brought
into contact countercurrently. The solvent re-
moves one or more components from the raw
gas, more or less selectively. The absorber is usu-
ally equipped with trays or packing to provide a
large gas – liquid contact area. The types most
frequently used are valve and sieve trays. Bubble
cap or tunnel trays are used only in special cases
(a comprehensive treatment of trays and pack-
ings used in absorption is presented elsewhere;
→ Absorption).
The solvent laden with the absorbed compo-
nents is withdrawn from the bottom of the ab-
sorber, routed to a regeneration system, where
it is freed of absorbed gas components, and re-
turned as lean solvent to the absorber. In most
gas treating processes, absorption is reversible,
and dissolved components are released chem-
ically unchanged during regeneration. Liquid-
phase oxidation processes for hydrogen sulfide
removal differ in this respect (see Section 5.4.3).
The different absorption processes are char-
acterized as physical or chemical depending on
whether gas components are simply dissolved
physically or are bound chemically to the sol-
vent. Typical equilibrium lines for chemical
and physical absorption are shown in Figure 40.
Loading capacity c (kilomoles per ton or per cu-
bic meter of solvent) is represented as a function
of the partial pressure of the dissolved compo-
nent. The loading in physical absorption, ini-
tially following Henry’s law, is almost directly
proportional to the partial pressure in the gas
phase, which results in a nearly linear equilib-
rium line. The equilibrium line in chemical ab-
sorption is bowed sharply during saturation of
the chemically active solvent component. After
saturation of the chemical capacity of the solu-
tion, only weak physical absorption in the sol-
vent’s main component (usually water) is pos-
sible which results in a steep linear equilibrium
curve.
At low partial pressure (e.g., p2 in Fig. 40) the
absorption capacity cch of the chemical solvent

is much higher than the absorption capacity cph
of the physical solvent, whereas the physical sol-
vent gives better results at high partial pressure,
(e.g., p1 ).
Figure 40. Gas – liquid equilibrium lines for (a) chemical
and (b) physical absorption
The strong dependence of physical solubility
on partial pressure can be utilized efficiently for
solvent regeneration by means of simple flash-
ing (i.e., pressure reduction). This improves the
economy of operation considerably, particularly
in case of bulk removal of impurities at high op-
erating pressure.
If the dissolved components are chemically
bound, less gas is released (∆cch < ∆cph ) when
the solvent is depressurized. Thus, regeneration
in chemical absorption processes is almost al-
ways accomplished by reboiling.
Fewer trays are generally required for chem-
ical absorption than for physical absorption due
to the acceleration of mass transfer by chemi-
cal reaction in the liquid phase and the low acid
gas equilibrium pressure over the solvent at low
loading.
Selection of Solvents. Selection of the appro-
priate solvent in a gas treating plant is most
important because the solvent circulation rate
determines equipment size and thus capital and
operating costs. The following simplified rules
are applicable, if linear dependence of the load-
ing capacity on partial pressure across the entire
concentration range in physical absorption and
Gas Production 91
saturation of a chemical solvent above a certain
partial pressure are assumed.
The solvent circulation rate required for phys-
ical absorption is largely independent of the
concentration of the component to be removed
but proportional to the total quantity G of crude
gas and inversely proportional to the total pres-
sure p and the absorption factor αi . The mini-
mum solvent circulation rate L min required to
remove component i completely can be esti-
mated from the component balance around the
absorber.
G
Lmin =
αi ·p
The solvent circulation rate for chemical ab-
sorption is proportional to the quantity of the
component to be removed and thus highly de-
pendent on the concentration of this component
in the gas, but practically independent of pres-
sure. The maximum allowable concentration of
the absorbed component in chemical solvents is
often set by practical limits like increasing cor-
rosion rate, increasing viscosity or tendency of
foaming at higher loading.
In addition to these basic rules, the follow-
ing points should be considered in selecting an
absorption process.
Achievable Purity. High product gas purity
can be obtained with many absorption processes,
but only a few are suitable from an economic
viewpoint. The minimum concentration of the
component to be removed in the clean gas is
mainly determined by the residual loading of
that component in the lean solvent fed to the
absorber top. Physical solvents can easily be re-
generated to low residual loadings by pressure
reduction and mild reboiling, whereas chemical
solvents require high energy input for reboiling
to achieve low loading.
Selectivity. The selectivity of a solvent is its
tendency to absorb primarily one or a group of
components from a gas mixture. Selectivity is
often defined as the concentration ratio of com-
ponent i to component j in the regenerator off-
gas to the concentration ratio of component i to
component j in the raw gas.
yi,off−gas yi,raw−gas
S= /
yj,off−gas yj,raw−gas
A high selectivity between the components
to be removed and the product gas components
is advantageous. High absorption rates of the
92 Gas Production
valuable product gas components reduce pro-
cess economy and may affect treatment of the
off-gas. If two or more components are to be re-
moved from the raw gas and these components
must be obtained separately, the solubility of the
various components in the solvent should be dif-
ferent so that the selectivity is high.
Utilities. For chemical absorption, cheap
low-pressure steam or waste heat with a suffi-
ciently high temperature is generally required,
whereas cheap electric power and cooling water
at low temperature are an advantage for physical
absorption.
Crude Gas Impurities. Impurities such as
carbonyl sulfide, carbon disulfide, hydrogen
cyanide, ammonia, mercaptans, thiophenes,
phenols, heavy hydrocarbons, metal carbonyls,
chlorides, and inorganic components such as
mercury directly influence selection of both sol-
vent and process [166]. Some trace compounds
of the raw gas can react with the solvent or other
absorbed compounds to form nonvolatile reac-
tion products, which cannot be removed dur-
ing regeneration. They accumulate in the sol-
vent circuit and can lead to operational prob-
lems like plugging, foaming, corrosion and to
solvent losses by degradation. Many commer-
cial solvents are not capable of removing organic
sulfur components and cyanide to the required
low levels to meet emission regulations or down-
stream process requirements. Raw gases from
coal gasification contain mercury which must be
trapped. The alternative to the selection of a sol-
vent which allows the removal of all these trace
components in the absorption process step is the
installation of a process chain consisting of COS
hydrolysis and cyanide conversion reactors and
adsorption guard beds.
Therefore trace components often determine
the suitability of a solvent.
Other Solvent Properties. If the raw gas has
to be dried or a low water dew point of the prod-
uct gas has to be achieved, absorption processes
using non-aqueous organic solvents are favor-
able. Aqueous chemical washes are preferable
when upstream process stages produce water as
a component of the treated gas mixture and this
water is required in the product gas downstream.
The laden and the lean solvent should be noncor-
rosive to avoid expensive materials of construc-
tion. High chemical and thermal stability reduce
solvent losses due to degradation and avoid ex-
pensive solvent reclaiming. Toxicity affects sol-
vent handling, storage, and safety equipment.
The solvent should be easily available on the
market.
The selection of an appropriate solvent can
be supported by computer tools such as AB-
SORPERT (Ruhr-University Bochum [167]).
This program contains heuristic rules, thermo-
dynamic properties of a large number of sol-
vents and a databank of industrial absorption
processes. All the information is linked to pro-
vide an expert system for a systematic solvent
selection and a basic process design based on
the information of the feed stream and the de-
sired separation.
Regeneration Methods. Absorption pro-
cesses with solvent recovery consist, in princi-
ple, of absorption and regeneration (desorption)
process steps. Several possible solvent regener-
ation methods are available; these are shown in
Figure 41.
The simplest and cheapest method is flash re-
generation (Fig. 41 A), in which the pressurized
laden solvent, is depressurized in one or more
stages. The residual content of dissolved com-
ponents depends on the pressure in the last stage;
therefore, this is often reduced to vacuum. Re-
generation efficiency can be increased consid-
erably by inert gas stripping (see Fig. 41 B). If
the inert gas is completely free of the gas to be
removed, the residual load of the solvent can be
reduced as desired, provided the volume of strip-
ping gas is large and the stripping rate is high
enough. It is, however, unavoidable that the re-
moved gas component is diluted by the inert gas.
This may be desirable in some cases, whereas
in others, further processing becomes economi-
cally prohibitive. Extremely high purity can be
obtained without using inert gas if the impuri-
ties are removed in a hot regeneration stage (Fig.
41 C). This method makes use of the fact that,
in general, the solubility of all gases decreases
sharply with increasing temperature. The sol-
vent is stripped by its own vapor, which is then
condensed from the overhead gas and recycled
as reflux. However, this method is rather costly
in terms of capital investment (1) because it re-
quires heat exchangers for the lean and laden
solvent and a regeneration column with reboiler
and condenser, and (2) because the utility de-
mand for heating and cooling is rather high.
 Gas Production 93

Figure 41. Absorption with different regeneration methods

A) Flashing; B) Stripping; C) Reboiling

Table 28. Absorption processes for acid gas removal

5.4.2. Processes for Carbon Dioxide and
Sulfur Compound Absorption [168 – 171] Trade name Solvent Licensor
Chemical absorption with aqueous amine solutions
MEA 1 – 3 N monoethanolamine free process
Numerous chemical and physical absorption DEA 2 – 4 N diethanolamine Elf Aquitaine
processes are available for removing carbon and others
DGA/ 4 – 6 N diglycolamine Fluor Daniel,
dioxide and various sulfur compounds from raw Econamine (2-(2-aminoethoxy)ethanol) Huntsman
gases. Hydrogen sulfide is the most widespread DIPA 2 N diisopropanolamine Shell and others
sulfur component and, like carbon dioxide, is an MDEA 2 – 5 N methyldiethanolamine free process
ADIP DIPA or MDEA Shell
acidic compound. Other sulfur impurities that
Amine formulated MDEA UOP/Union
may be present in a raw gas are carbonyl sulfide, Guard/ Carbide
carbon disulfide, mercaptans, and thiophenes. A Ucarsol
aMDEA MDEA + activator for enhanced BASF
summary of chemical and physical absorption CO2 absorption
processes is given in Table 28. Gas Spec formulated MDEA DOW Chemical
Physical absorption processes are used pre- Flexsorb hindered amine Exxon
dominantly to remove carbon dioxide and hy-
Chemical absorption with alkaline solutions (hot potassium
drogen sulfide from gases with high carbon diox- carbonate)
ide partial pressure, especially converted gases Benfield K2 CO3 + activator (DEA) UOP
produced in partial oxidation plants based on Catacarb K2 CO3 + catalyst Eickmeyer
Giammarco- K2 CO3 + activator (arsenic Giammarco
coal or residual oil. Here the partial pressure Vetrocoke trioxide)
of carbon dioxide is above the level appropriate Vacasulf K2 CO3 + NaOH Krupp Uhde
for economic application of chemical absorption
Physical absorption
systems. Rectisol methanol Linde/Lurgi
Chemical absorption process (normal amine Selexol polyethylene glycol dimethyl UOP
based) are used widely, especially for crude gas ether (DMPEG)
containing carbon dioxide and hydrogen sulfide Purisol N-methyl-2-pyrrolidone (NMP) Lurgi
Morphysorb N-formylmorpholine (NFM) Krupp Uhde
at low partial pressure. As shown above, various
amines are employed. The selection of amine is Physical – chemical absorption
influenced by specific process conditions such as Sulfinol D/M sulfolane (tetrahydrothiophene Shell
oxide) + DIPA or MDEA
the presence of further impurities in the raw gas, Amisol methanol + MEA, DEA or DETA Lurgi
which may cause solvent degradation, corrosion
and foaming. Low coabsorption of valuable gas
components in the aqueous amine solution is an Sulfur components like hydrogen sulfide,
advantage of all amine processes. carbonyl sulfide, and mercaptans have a higher
solubility in physical solvents than carbon diox-
94 Gas Production
ide. This facilitates production of a sufficiently
hydrogen sulfide rich gas for the sulfur recovery
process. Compared to aqueous amine solutions,
selectivity with regard to valuable components
is lower in organically based physical solvents,
which leads to higher losses of these compo-
nents.
Amine solutions do not show a selectivity of
hydrogen sulfide over carbon dioxide at equilib-
rium. Therefore, very high sulfur purity can be
obtained only if carbon dioxide is removed si-
multaneously to a very low level. However, the
reaction rate of certain amines with hydrogen
sulfide is much higher than with carbon dioxide.
Hydrogen sulfide can therefore be selectively re-
moved by utilizing this difference in reaction
kinetics. In the absorber a large gas liquid inter-
facial area has to be provided for a fast hydrogen
sulfide mass transfer to achieve the required low
sulfide concentration in the purified gas. Simul-
taneously a short contact time between gas and
liquid is required so that only a small portion of
the absorbed carbon dioxide can react with the
amine [172].
Figure 42. Equilibrium curves of CO2 in various solvents
a) H2 O (30 ◦ C); b) N-methyl-2-pyrrollidone (40 ◦ C);
c) Methanol (− 15 ◦ C); d) Methanol (− 30 ◦ C); e) Hot
potassium carbonate solution (110 ◦ C); f) Sulfinol solution
(50 ◦ C); g) 2.5 M Diethanolamine solution (50 ◦ C); h) 3 M
Amisol DETA solution
In an attempt to combine the advantages
of chemical and physical absorption, processes
using chemical absorbents mixed with or-
ganic solvents have been developed. These pro-
cesses, termed physical – chemical absorption
processes or mixed solvent processes, are suit-
able both for absorbing carbon dioxide and hy-
drogen sulfide and for removing organic sulfur
compounds, giving high end purities. A survey
of the equilibrium behavior of carbon dioxide in
common solvents is shown in Figure 42.
Initial selection of a gas purification process
based on the partial pressure of the acid gas in
the raw gas versus the product gas specification
can be done with the aid of Figure 43.
Figure 43. Selection of appropriate gas purification process
for simultaneous H2 S/COS and CO2 removal
If the acid gas partial pressure in the raw gas
is very low, dry-bed adsorption processes (e.g.,
solid beds of zinc oxide, iron oxide, activated
carbon, or molecular sieves) or nonregenerable
scavenger solutions are used for gas cleaning.
5.4.2.1. Physical Absorption Processes
Water was an industrially important solvent for
carbon dioxide absorption, particularly in am-
monia synthesis, until organic solvents were in-
troduced. Organic solvents have a much higher
solvent capacity than water, which improves
process economy.
Organic solvents are especially suitable for
treating converted raw gases obtained from par-
tial oxidation of oil or coal. The carbon dioxide
partial pressure in these gases can be as high
as 2.5 MPa. At this high acid gas partial pres-
sure the solvent capacity, i.e. solvent loading,
 Gas Production 95

of organic solvents exceeds that of chemical ab-

sorbents considerably.

Rectisol Process. The Rectisol process, in-

vented by Lurgi around 1950 and developed
further together with Linde, is particularly suit-
able for the specific requirements of high-pres-
sure synthesis gas production [173].This process
achieves syngas quality with very low total sul-
fur content in the ppb range and removal of all
impurities and bulk CO2 in one process step.
More than 60 Rectisol units were reported to
be operating worldwide in 2005 purifying more
than 210 × 106 m3 /d (STP) of synthesis gas,
which is equivalent to more than 75 % of the gas
produced from coal, oil, and waste gasification.
Originally designed and applied in conjunc-
tion with Lurgi pressure gasification of coal, the
Rectisol process is now also used successfully
in oil-based synthesis gas plants and other coal
gasification processes, as well as in special cases
of natural gas treatment.
The Rectisol process uses cold methanol as
Figure 44. Absorption coefficient λ of various gases in
solvent. The solubility of acid gas in metha- methanol at low pressure (1 bar)
nol increases strongly with decreasing tempera-
ture whereas the solubility of the valuable light
components is almost temperature independent. Standard Rectisol Process. In gas produc-
Temperatures as low as − 75 ◦ C are therefore tion, the Rectisol process is used in two basic
applied in order to minimize the required solvent configurations: the nonselective standard pro-
circulation rate and the loss of valuable gas com- cess and the selective process configuration. All
ponents. The low operation temperature also re- acid gas constituents are absorbed simultane-
duces solvent losses into the product streams by ously in the standard Rectisol process. The basic
lowering the vapor pressure of methanol. Good flow diagram of the standard process with two
mass and heat transfer are provided by methanol absorption sections is shown in Figure 45. Flash-
due to its low viscosity. Operating the process regenerated methanol, fed to the lower part of the
at low temperature does not necessarily require absorber, largely removes hydrogen sulfide and
large refrigeration units. The major part of the carbon dioxide at bottom temperatures between
cooling is done by internal heat exchange and − 10 to − 30 ◦ C. The remaining hydrogen sul-
by utilizing the temperature decrease by gas de- fide and carbon dioxide are removed from the
sorption and expansion. In Figure 44, the tem- gas to the required purity by heat-regenerated
perature dependence of the absorption coeffi- cold methanol in the absorber top section.
cient λ, which is defined by c = λp, is shown Under these process conditions, solvent load-
for various gases at 1 bar. The absorption coef- ing is very high at the bottom of the absorber,
ficient is not entirely pressure-independent but which results in a low solvent rate. The heat
rises above the value measured at 1 bar as the of absorption raises the temperature of the sol-
partial pressure of the gas approaches its satu- vent; the absorber bottom temperature may be as
ration vapor pressure. The nonideal behavior of much as 50 ◦ C higher than the solvent inlet tem-
the gas phase at higher total pressure also must perature. During flash regeneration of the sol-
be considered to model the gas liquid equilibria vent, this heat of absorption is given off. and the
correctly (→ Absorption). solvent temperature drops accordingly. The ap-
plied low absorption temperatures are generated
96 Gas Production
Figure 45. Standard Rectisol process for simultaneous removal of H2 S and CO2
a) Absorber; b) Flash tower; c) Hot regeneration; d) Condenser; e) Methanol – water column
in this desorption step and not by the refrigera-
tion unit. This phenomenon is often referred to
as the “autorefrigeration effect”. In the fine wash
section of the absorber, only the residual acid
gases are removed. Therefore, little heat of ab-
sorption is released in the fine wash section and
the temperatures remain low. Moreover, there is
a smaller quantity of gas to be treated in the fine
wash section. Therefore, solvent demand in the
fine wash section is considerably lower than that
in the main section of the absorber. This is de-
sirable in view of the high investment and utility
costs for hot regeneration.
In Fischer – Tropsch synthesis, SNG, and
town gas plants, carbon dioxide must only be re-
moved to a final content of 1 – 2 %. This value
can even be reached in the main wash part with
flash-regenerated methanol. The fine wash part
then has to be designed only for removal of hy-
drogen sulfide and carbonyl sulfide, which re-
sults in a lower solvent rate, normally one-tenth
of the total amount of solvent withdrawn from
the bottom, due to the higher solubility of these
components.
Downstream of hot regeneration, a metha-
nol – water distillation column is used to sepa-
rate water entering with the raw gas. To prevent
icing in the cooling section of the raw gas, a
small amount of methanol is injected upstream
of the heat exchanger. The mixture of methanol
and water is withdrawn and fed directly to the
distillation column. A refrigeration unit is used
to cover cold losses in the plant due to surge
energy, incomplete heat exchange, unrecovered
heat of absorption, and insulation losses. An am-
monia absorption refrigeration unit can be ad-
vantageously applied if low temperature (130 –
200 ◦ C) waste heat is available.
The standard Rectisol process combines all
absorbed gases in a single acid gas stream. The
sulfur compounds are thus diluted with the entire
absorbed volume of carbon dioxide. (Referred
to the raw gas specification in Table 24, only 0.9
vol % of hydrogen sulfide [example 2] and only
1.8 vol %, of hydrogen sulfide [example 4] in the
off-gas are typical of the standard process with
complete removal of carbon dioxide.) The off-
gas with this low sulfur content is not suitable
for sulfur recovery in a Claus process. Other sul-
fur recovery processes must be applied such as
liquid-phase oxidation (see 5.4.3) or adsorption.
The standard Rectisol process is therefore ad-
vantageously applied for gases from low-sulfur
feedstock.
Selective Rectisol Process. Initially the se-
lective Rectisol process was introduced to pro-
duce an off-gas rich in hydrogen sulfide which
could be processed in a Claus plant for sulfur
recovery. Pure carbon dioxide is produced as a
second product with a total sulfur content in the
low ppm range. This stream can be vented to at-
mosphere or utilized, for example in urea plants,
which are often built in conjunction with ammo-
nia plants, or recovered in food grade (see Sec-
tion 6.3),or can be used for enhanced oil recov-

Figure 46. Selective Rectisol process for separate removal and recovery of H2 S and CO2
a) H2 S absorption; b) CO2 absorption; c) Flash regeneration; d) Stripper; e) Reabsorber; f) Hot regeneration
ery and sequestration. The solvent loops shown
in Figure 45 are interchanged for that purpose
(see Fig. 46). The raw gas is first desulfurized
with a small amount of heat-regenerated metha-
nol. The carbon dioxide coabsorption is low be-
cause of its low solubility and the presaturation
of methanol in the carbon dioxide absorption
column.
Most of the carbon dioxide and the remain-
ing traces of sulfur compounds are removed in
the downstream carbon dioxide scrubber in two
stages, by using flash-regenerated methanol in
the middle section and heat-regenerated metha-
nol in the top section.
Depending on the requirements, carbon diox-
ide may be removed down to a few percent or
even a few parts per million. Removal of both
carbonyl and hydrogen sulfides as well as mer-
captans to 0.1 ppm is ensured in all cases.
According to Figure 44, the selectivity bet-
ween carbon dioxide and hydrogen sulfide for
the raw gas indicated in column 4 of Table
24 is not sufficiently high to give an off-gas
rich enough in hydrogen sulfide for the Claus
process. Therefore, an additional concentration
Gas Production 97
stage is required before the solvent passes to hot
regeneration. In the bottom section of the reab-
sorber column (d in Fig. 46) carbon dioxide is
stripped out of the laden solvent by simple pres-
sure reduction or stripping with inert gas. In the
top section (e) the small amount of hydrogen sul-
fide which is stripped together with the carbon
dioxide in the bottom section is reabsorbed with
methanol to yield a sulfur-free off-gas.
In the selective Rectisol process, much more
solvent must be treated by hot regeneration
than in the standard Rectisol process. Additional
methanol is required in the reabsorber, and more
methanol is necessary in the hydrogen sulfide
absorber because the entire gas rate must be
treated at higher temperature.
To avoid the extra load on the regeneration
unit, the two Rectisol wash steps can be sep-
arated by removing the sulfur compounds up-
stream of carbon monoxide conversion, with car-
bon dioxide removal located downstream of the
conversion unit. The solvent loops of both ab-
sorption steps are still combined. A classic ap-
plication of this case is synthesis gas production
by residual oil gasification.
98 Gas Production

As shown in Table 24, example 3, the ratio

of hydrogen sulfide to carbon dioxide upstream
of shift conversion is approximately ten times
higher than downstream (example 4). Therefore,
the natural selectivity of methanol is sufficient to
produce a sulfur-rich off-gas suitable for sulfur
recovery in a Claus process. In addition, the gas
rate upstream of carbon monoxide conversion
is only 70 % of the rate downstream; therefore,
less solvent is required for desulfurization. This
simplification of the gas treating unit, combined
with the advantage of passing a sulfur-free gas
to the carbon monoxide conversion unit and the
possibility to apply low-temperature shift con-
version for minimum residual carbon monoxide
in the raw hydrogen, must be paid for by cooling
the gas twice.
Because the selective Rectisol process is
much more complex than the standard process,
a decision must be made in each individual case
as to which route gives the most economical so-
lution in conjunction with the downstream plant Figure 47. Two train selective Rectisol plant downstream
and the sulfur recovery unit. of residual oil gasification producing 40 000 m3 /h (STP)
For Fischer – Tropsch synthesis and SNG gas for oxo synthesis from unshifted gas and 30 000 m3 /h
plants based on coal with a low sulfur content (STP) hydrogen from shifted raw gas (Courtesy of Celanese
and Lurgi AG)
(example 2 in Table 24; pure carbon dioxide is
not required in either case), the standard Rectisol
process has mostly been used, with the off-gas The selective process is used with two sep-
being treated in a special chemical system. arate absorption steps for raw and converted
A two train Rectisol plant is shown in Figure gas from oil and coal gasification by partial ox-
47. Part of the raw gas from a residual oil gasifi- idation processes. Absorber – stripper systems
cation is shifted and purified in the first train to (Fig. 41) are used to remove small quantities of
produce pure hydrogen. The remaining raw gas carbon dioxide and hydrogen sulfide as integral
is purified in the second train giving gas for oxo parts of low-temperature units.
synthesis. The solvent of both trains is regener- Plants with a one train throughput of more
ated in a common hot regenerator column. than 15.6 × 106 m3 (STP)/d are already oper-
Applications [174, 175]. In view of (1) the ating. The utility requirements for a Rectisol
high flexibility with regard to carbon dioxide, unit vary widely depending on process condi-
hydrogen sulfide, and carbonyl sulfide removal, tions. Typical consumption figures for selective
as well as the removal of various trace com- removal of hydrogen sulfide and carbon diox-
pounds, (2) the high purity of the treated gas, ide from raw gas, yielded by partial oxidation
and (3) the absence of corrosion at low tempera- relative to 100 000 m3 (STP)/h (H2 and CO) are
ture, the Rectisol process is used in the following
Power for drive shaft
cases: (without power 2000 – 2500 kW
Standard processes are used for raw and con- recovery)
verted gas from coal gasification (in this case, Steam (0.5 MPa) 5 – 7 t/h
combination with prewash systems for other im- Waste heat above 33 – 42×106 kJ/h using absorption
110 ◦ C
purities is also possible). Cooling water (∆t = 3
1500 – 2000 m /h refrigeration
Selective processes with two absorption 10 ◦ C)
steps immediately following are used for raw and Methanol 60 – 70 kg/h

converted gas from coal or oil gasification plants.


The application of the Rectisol Process for
hydrogen production and for Integrated Gasifi-
cation Combined Power Cycles (IGCC) [176]is
described in 5.4.2.4(see Sections 7.2 and 7.3).
Processes with Other Physical Solvents.
The Rectisol process needs a refrigeration unit to
maintain the low absorption temperatures. Other
processes employ organic solvents with high
boiling points and low vapor pressures. These
solvents provide a high absorption capacity for
acid gases at ambient or slightly subambient
temperature without appreciable vapor losses.
Although higher absorption temperature low-
ers carbon dioxide solubility, at a high partial
pressure of carbon dioxide the loading capacity
of organic solvents is still attractive and simi-
lar to the capacity of chemical solvents under
comparable conditions.
Processes using high-boiling organic sol-
vents are
1) Selexol process developed by Allied Chemi-
cal Corporation (now licensed by Norton and
UOP) and the Genosorb process of Clariant
and Krupp Uhde, all using a mixture of di-
methyl ethers of polyethylene glycol (DM-
PEG);
2) Purisol process, developed by Lurgi, using N-
methyl-2-pyrrolidone (NMP);
3) Fluor solvent process using propylene carbon-
ate (PC);
4) Morphysorb process developed by Krupp
Uhde using N-formylmorpholine (NFM);
5) Sepasolv process by BASF applying a mix-
ture of oligoethylene glycol methyl isopropyl
ethers (MPE); and
6) the Gaselane process using N-methylcapro-
lactam (NMC) developed by VEB Leuna
[178]
The normal boiling point of these solvents is
between 200 and 350 ◦ C; their relative molec-
ular mass, between 100 and 320. The solubility
of carbon dioxide is similar for all solvents.
If selective removal of hydrogen sulfide from
gas containing carbon dioxide is required, NMP
is superior to Selexol, Sepasolv, and propylene
carbonate. The solubility of carbonyl sulfide in
all solvents is remarkably lower than the solu-
bility of hydrogen sulfide.
This means that if these processes are used to
purify gases containing both carbonyl and hy-
Gas Production 99
drogen sulfides to synthesis gas quality, a car-
bonyl sulfide hydrolysis step is generally re-
quired. With regard to removal of carbon dioxide
from sulfur-free synthesis gas, the process flow
sheet is basically the same for all processes, con-
sisting of a simple absorber – stripper system. In
addition to nitrogen or other inert gases, air is a
suitable stripping medium.
Selexol Process [177]. This process was de-
veloped by Allied Chemical Corporation and
is now licensed by Norton and UOP. The Se-
lexol solvent is a trademark of the DOW Chem-
ical Company and consists of a mixture of di-
methyl ethers of polyethylenglycol (DMPEG).
A similar mixture of DMPEG is used as sol-
vent in the Genosorb process of Krupp Uhde
and Clariant (solvent supplier). More than 50
Selexol plants had been constructed by 2005
purifying more than 110 × 106 m3 /d (STP) of
natural gas and synthesis gas. Most commercial
applications of the Selexol process are for treat-
ing natural and synthesis gas with high contents
of hydrogen sulfide and carbon dioxide or high
concentrations of carbon dioxide alone [175].
To purify gases containing carbon dioxide and
hydrogen sulfide, the process may be used for
either bulk removal of both components or se-
lective removal of hydrogen sulfide, with the de-
sired quantity of carbon dioxide being retained
in the lean gas. Whereas the solubility of hydro-
gen sulfide is approximately nine times that of
carbon dioxide, the solubility of carbonyl sulfide
is only twice that of carbon dioxide.
This means that the difference in solubility
between hydrogen sulfide and carbon dioxide
is large enough to provide a good basis for se-
lective absorption of the former. The solubility
difference between carbonyl sulfide and carbon
dioxide, on the other hand, is less favorable.
If carbonyl sulfide must be removed together
with hydrogen sulfide, the solvent picks up more
carbon dioxide and the feed to the Claus unit will
be diluted with more carbon dioxide than for re-
moval of hydrogen sulfide alone. Hydrolyzing
carbonyl sulfide upstream of the absorption pro-
cess can circumvent this problem. Nearly total
conversion of carbonyl to hydrogen sulfide can
be attained by vapor-phase catalytic hydrolysis,
leaving only hydrogen sulfide and carbon diox-
ide as key components.
A certain amount of water in the Selexol sol-
vent does not greatly decrease the solubility of
100 Gas Production
acid gases. Thus, in the case of hot regeneration
by reboiling under normal pressure, the boiling
point of the solvent can be decreased by addition
of a suitable quantity of water.
A disadvantage of the Selexol solvent is that
its lower boiling components are distilled off.
Care must be taken that solvent properties do
not change in the course of time.
The Selexol process is applied for following
purposes:
1) Selective removal of hydrogen sulfide from
natural gas and synthesis gas
2) Removal of high carbon dioxide content to a
low residual level from natural gas and syn-
thesis gas
3) Purification of landfill gas
Purisol Process. The Purisol process applies
a mixture of NMP and water as solvent. It can
be operated either at ambient temperature or
— in conjunction with a refrigeration unit — at
temperatures down to ca. − 15 ◦ C. The Purisol
process has been operated successfully for sev-
eral decades in selective natural gas desulfuriza-
tion and bulk CO2 removal from converted syn-
thesis gas. The process has the advantage of a
higher hydrogen sulfide – carbon dioxide selec-
tivity than Selexol, permitting the production of
sulfur-rich Claus gas with about 50 % hydrogen
sulfide, even if the ratio of carbon dioxide to hy-
drogen sulfide in the raw gas reaches extremely
high values.
The solubility of carbonyl sulfide is only 20 %
that of hydrogen sulfide, but the former is partly
hydrolyzed to the latter by the NMP solvent re-
sulting in a 60 – 80 % carbonyl sulfide removal.
If the absorber is designed with carbonyl sul-
fide reaction zones, COS can be removed quan-
titatively. The absorption of valuable gas com-
ponents is approximately 10 % lower compared
to Selexol. Therefore a smaller amount of flash
gases has to be recompressed.
For carbon dioxide removal, the NMP sol-
vent can be regenerated with air, if nitrogen is
not available. The carbon dioxide concentration
in the purified gas can be reduced to 1000 ppm
or less, with almost no steam demand for regen-
eration.
A typical example of a Purisol unit for remov-
ing carbon dioxide from converted gas is shown
in Figure 48. Two identical units of this type op-
erate in the same plant, treating synthesis gas for
hydrogen production.
Pre- and afterwash steps are shown for both
the absorber and the stripper in the flow sheet of
Figure 48. Initially, raw and stripping gases are
dried with a small amount of NMP to keep the
water content of the solvent in the carbon diox-
ide absorption section low. A water wash on top
of the columns reduces NMP losses. In general,
NMP recovery with water is not necessary if the
Purisol process is operated at subambient tem-
perature. If a low water dew point of the product
gas is required, NMP can be recovered by means
of a glycol afterwash step.
The water – NMP mixture is separated in a
third column, which simultaneously recovers
NMP from the carbon dioxide off-gas at the flash
stage. Carbon dioxide itself reduces the boiling
point of the NMP – water mixture, which is a
desirable effect.
Applications. The Purisol process is excel-
lently suited to fours typical applications for
high-pressure gases:
1) Selective removal of hydrogen sulfide
2) Removal of high carbon dioxide content to a
low residual level
3) bulk removal of acidic compounds down to
moderate product purity by using a simplified
flash regeneration system, and
4) Removal of organic sulfur components (mer-
captans)
Fluor Solvent Process. In the late 1950s, the
Fluor solvent process using propylene carbonate
was commercialized by Fluor and El Paso [180].
Removal of carbon dioxide from natural gas at
mildly subambient temperature was the first ap-
plication. The main criterion for selecting PC
in the Fluor solvent process was its high carbon
dioxide solubility, together with a relatively low
solubility of methane. Propylene carbonate has
limited water solubility, and slowly reacts irre-
versibly with water and carbon dioxide around
90 ◦ C. Thus, it is unsuitable for controlling the
water content by distillation under atmospheric
pressure. Pre- or afterwash steps are, therefore,
not applicable.
Morphysorb [181, 182]. Krupp Uhde ap-
plied their experience with N-formyl morpho-
line (NFM) as solvent to develop the Mor-
physorb process for selective sulfur compounds
removal and bulk CO2 absorption. Lower meth-

Figure 48. Purisol process for CO2 removal from high pressure converted gas
a) Absorber; b) Stripper; c) NMP-water separator
ane solubility compared to other commercial
solvents is claimed. NFM has a freezing point
of 23 ◦ C. To take advantage of the higher acid
gas solubility at lower temperatures a mixture of
NFM and N-acetyl-morpholine (NAM) is pro-
posed.
5.4.2.2. Chemical Absorption Processes
Amine Processes. Aqueous amine solutions
have been used on an industrial scale for the
absorption of carbon dioxide and hydrogen sul-
fide for a long time. They are especially suited
for gases with low organic sulfur content and
less stringent purity requirements regarding hy-
drogen sulfide, as for example natural gas of
pipeline quality or fuel gases. Synthesis gas
qualities with total sulfur contents below 1
mL/m3 require an additional sulfur adsorption
guard bed downstream of the amine absorber.
Mono- and diethanolamine (MEA, DEA),
as well as diglycolamine (DGA, 2-(2-
aminoethoxy)ethanol), diisopropanolamine
(DIPA), and methyldiethanolamine (MDEA),
are well known in this field. Several so-called
formulated amines are available on the market
such as Ucarsol, Gas-Spec, and aMDEA (see
Table 28). These solvents contain specific addi-
tives in order to allow higher amine concentra-
tions, to enhance carbon dioxide absorption rate
and to reduce corrosion potential and foaming
Gas Production 101
tendency. The selectivity of the solvent towards
hydrogen sulfide can be improved by sterically
hindered amines such as Flexsorb SE.
Alkanolamines can be regarded as derivatives
of ammonia in which one, two, or three hy-
drogen atoms have been replaced by a Cn H2n -
OH group. According to the number of or-
ganic groups attached to the nitrogen atom they
are classified as primary, secondary, and ter-
tiary alkanolamines. The primary alkanolamines
applied for gas treating contain one ethanol
group (MEA) or one glycolic group (DGA)
The secondary alkanolamines employed contain
two ethanol (DEA) or isopropyl alcohol groups
(DIPA). MDEA as an N-alkylated alkanolamine
has two ethanol groups and one methyl group
attached to the nitrogen. The amino group pro-
vides the necessary alkalinity in the water so-
lution to absorb the acid gases. The hydroxyl
group in the alcohol moiety increases the water
solubility and reduces the amine vapor pressure.
In the amine processes the acid gas compo-
nents react reversibly with the alkaline solvent.
The reactions of hydrogen sulfide and carbon
dioxide with amines can be represented as fol-
lows:
Reaction of amine and water (protonation):
R1 R2 R3 N+H2 OR1 R2 R3 NH+ +OH−
Sulfide formation:
H2 S+R1 R2 R3 NR1 R2 R3 NH+ +HS−
102 Gas Production
Carbamate formation:
CO2 +2 R1 R2 R3 NR1 R2 NCOO− +R1 R2 R3 NH+
Bicarbonate formation:
CO2 +OH− HCO−
3
Hydrogen sulfide reacts instantaneously with
all amines to form sulfide. Carbon dioxide can
only react with primary and secondary amines to
form carbamate. The carbamate reaction rate has
a moderate velocity. The bicarbonate formation
is slow. The different reaction rates of hydrogen
sulfide and carbon dioxide with the amines are
the basis for selective hydrogen sulfide absorp-
tion. MDEA has a higher selectivity compared
to primary and secondary amines since no carb-
amate is formed with tertiary amines and carbon
dioxide can only be absorbed via the slow bicar-
bonate reaction. In order to utilize this selectiv-
ity based on the reaction kinetics, the absorber
must provide sufficient mass transfer area for
complete hydrogen sulfide removal in combina-
tion with short residence time to suppress carbon
dioxide absorption [183].
When the temperature of the solvent is in-
creased and the pressure reduced, the chemical
equilibrium of the above equations is shifted to
the left side and the acid gases are released.
The flow diagrams for all amine process are
basically the same (Fig. 49). Feed gas is brought
in contact with the solvent in an absorber (a).
Laden solvent flows through a heat exchanger
(d) to the regeneration system (e), in which acid
gases are desorbed from the solvent at reduced
pressure with vapor generated by reboiling. Acid
gases leave the regenerator overhead after the
stripping steam has condensed (f). Regenerated
solvent is returned to the absorber by way of
the solvent heat exchanger (d) and solvent cooler
(b). Amine losses with the lean gas have to be
reduced by a water wash step. If the absorption
operates at elevated pressure it is often econom-
ical to recover the absorbed valuable gases in
an additional flash stage downstream of heat ex-
changer (d).
The amine concentration determines the ca-
pacity of the solvent and thus the solvent circula-
tion rate. The maximum amine concentration of
the solution is limited with regard to corrosivity
of the rich solvent, viscosity, and other proper-
ties. Alkanolamines are susceptible to degrada-
tion by several trace components present in the
raw gas and by carbon dioxide. Carbon dioxide
catalyzes the degradation of MEA and DEA to
form heat stable salts and inactive polymer reac-
tion products, which increase solvent viscosity
and foaming tendency. DIPA reacts with carbon
dioxide to form oxazolidone. The capacity of the
primary and secondary amines has to be main-
tained by continuous solvent reclaiming. MDEA
as tertiary amine and hindered amines, which do
not form carbamates, are not affected by carbon
dioxide.
Figure 49. Basic flow diagram for amine processes
a) Absorber; b) Solvent cooler; c) Solvent pump; d) Heat
exchanger; e) Regenerator; f) Condenser; g) Reboiler
Carboxylic acids (e.g., formic acid, acetic
acid, oxalic acid) are frequently found in amine
solvents. They are formed directly from cyanide
and by degradation of the amine with oxy-
gen. At high carbon monoxide partial pressure
formic acid is directly produced in alkaline so-
lutions. Carboxylic acids tie up amines as heat
stable salts (HSS). Sulfur dioxide also reacts ir-
reversibly with the amine to form HSS. Heat sta-
ble salts reduce solvent capacity and are a major
source of corrosivity [184]. Common practice
is the addition of caustic soda to liberate the
amine and to restore solvent capacity. The ef-
fect of caustic addition on the corrosivity of the
solvent is small because the acid anions remain
in the solution [185]. The salts of the carboxyl-
ic acids have to be removed by ion exchange or
distillation.
Primary Amines. Solutions of MEA were
used almost exclusively for many years to re-
move hydrogen sulfide and carbon dioxide from
natural gas and certain synthesis gases because
of their high reactivity and the high purity ob-
tainable.

The disadvantages of MEA are the forma-
tion of nonregenerable and corrosive degrada-
tion products with carbonyl sulfide and carbon
disulfide. Because of the high vapor pressure
of MEA a water wash step of the purified gas
is normally required. The high heat of reaction
causes high steam demand for hot regeneration.
Thus MEA units are rapidly being replaced by
other systems. However, the MEA solution is
still preferred for gas streams containing small
amounts of hydrogen sulfide and carbon diox-
ide with practically no carbonyl sulfide or car-
bon disulfide (e.g., the removal of carbon diox-
ide from reformed gas produced in a tubular re-
former).
Newly developed corrosion inhibitors allow
aqueous concentration of 30 wt % MEA, which
results in a lower solvent circulation rate. An ex-
ample is the Amine Guard process from Union
Carbide. The Amine Guard process is suitable
only for removal of carbon dioxide because sul-
fur components react with the inhibitors.
DGA is used in Fluor’s Econamine process.
The high DGA concentration (typical 40 – 60
wt %) reduces the required solvent circulation
rate compared to MEA. Carbonyl sulfide is par-
tially removed from the gas and the degradation
products of DGA can be reclaimed at elevated
temperature. No water wash step is required due
to its lower vapor pressure [186].
Secondary amines DEA and DIPA are
widely used to treat refinery gases and high
pressure natural gases.
DEA is applied in the 20 – 25 wt % concen-
tration range for refinery applications. DEA is
superior to MEA for treating of refinery gases,
which contain appreciable amounts of carbonyl
sulfide and carbon disulfide, because DEA reacts
with these components to a much lesser extent
and the reaction products are less corrosive. The
SNEA-DEA process for natural gases was devel-
oped by Societé National Elf Aquitaine (SNEA)
[187]. A 25 – 30 wt % DEA solution is used re-
sulting in higher solvent capacity. Acid gas load-
ings up to 0.7 – 1 mol/mol of DEA is possible
with sufficiently high acid gas partial pressure.
The heat of reaction of DEA and carbon dioxide
is about 25 % lower than that of MEA and car-
bon dioxide. Therefore, DEA solutions require
less steam for hot regeneration.
The ADIP process of Shell International Oil
Products, licensed by JGC, Stork Engineers &
Gas Production 103
Contractors, and Chiyoda [188], utilizes DIPA
in concentrations up to 50 wt %. ADIP units are
suitable for sweetening natural gas, refinery gas,
and Claus tail gas. MDEA is also used in ADIP
units if higher hydrogen sulfide selectivity is re-
quired. DIPA is claimed to be more stable against
degrading and corrosive trace components like
cyanide, oxygen, and sulfur dioxide than MDEA
[212]. Therefore in cases where selectivity is not
critical, DIPA is the preferred solvent for hydro-
gen sulfide removal. Raw gas purification and
Claus tail-gas treatment can be integrated into
one plant (Fig. 50). One single regeneration col-
umn (d) provides lean amine solvent for the fine
wash section of the high pressure absorber (a)
and the Claus tail-gas absorber (e). The tail-gas
absorber operates at low pressure and hydrogen
sulfide has to be removed selectively to avoid a
large carbon dioxide recycle through the Claus
plant. Therefore the rich solvent leaving the tail-
gas absorber is not completely saturated and can
absorb acid gas in the lower section of the high
pressure absorber (a).
Hydrogen sulfide concentrations in the puri-
fied gas below 5 ppm (mL/m3 ) are achievable
with DIPA since it is easier to regenerate with
less steam than MEA and DEA. DIPA has a
lower tendency to form corrosive degradation
products than DEA.
Tertiary Amines. MDEA is the most widely
used tertiary amine. It is suitable to purify a large
variety of gases. The carbon dioxide absorption
rate is slower in tertiary amines because they do
not form carbamates This makes MDEA partic-
ularly suited for selective hydrogen sulfide re-
moval from gases with elevated carbon diox-
ide contents. Many formulated MDEA based
amines are available on the market, which are
claimed to have improved hydrogen sulfide se-
lectivity (e.g., Gas Spec, Ucarsol) [189]. The low
heat of reaction facilitates regeneration down to
low acid gas contents in the lean amine required
to achieve hydrogen sulfide concentrations be-
low 5 mL/m3 in the purified gas. MDEA is ap-
plied in the 30 – 50 wt % range. Acid gas load-
ings up to 0.8 mol/mol of MDEA is possible in
carbon steel equipment. The high MDEA con-
centration in conjunction with the high attain-
able acid gas loading result in a high capacity
of the solvent and a low solvent circulation rate.
For this reason many amine units originally de-
signed and operated with primary or secondary
104 Gas Production
Figure 50. Integration of high pressure gas purification with Claus tail-gas treating
a) High pressure absorber; b) Solvent heat exchanger; c) Flash drum; d) Regenerator; e) Claus tail-gas absorber; f) Solvent
cooler; g) Amine filter
amines were converted to use MDEA as solvent
in order to increase plant capacity and reduce
utility consumption [190]. As a guideline, the
steam required for regeneration per volume sol-
vent is approximately 80 kg/m3 for bulk carbon
dioxide removal and 120 kg/m3 for selective hy-
drogen sulfide removal.
MDEA is widely used in refineries for hydro-
gen sulfide absorption from various medium- to
high-pressure off-gas streams from hydrotreat-
ing units and the hydrocracker. MDEA is also
suitable for selective absorption of hydrogen sul-
fide from low-pressure gases and is therefore ap-
plied in the Claus tail gas treating process.
The carbon dioxide absorption rate in MDEA
solutions is enhanced by addition of small
amounts of primary and secondary amines
[191]. This effect is employed for example in
the aMDEA process of BASF and the activated
MDEA process of Elf Aquitaine. The carba-
mate formed with the activator component is hy-
drolyzed, giving bicarbonate and recovering the
activator. The consecutive carbamate formation
and hydrolysis reactions are much faster than
direct bicarbonate formation with water.
Activator-carbamate reaction:
CO2 +R1 R2 NHR1 R2 NCOO− +H+
Carbamate hydrolysis:
R1 R2 NCOO− +H2 OR1 R2 NH+HCO−
3
Part of the absorbed carbon dioxide can be
liberated from aqueous MDEA solution by pres-
sure reduction. Flash regeneration is sufficient
if only bulk carbon dioxide removal is required.
Lower carbon dioxide concentrations in the pu-
rified gas are achievable with an additional fine
wash section, which has to be fed only with a
small stream of steam regenerated solvent (Fig.
51). This makes the activated MDEA process at-
tractive in terms of steam consumption. A typ-
ical aMDEA plant for the removal of carbon
dioxide from steam reformer gas is shown in
Figure 52.
The largest acid gas absorbers were built for
a liquefied natural gas (LNG) terminal with a
single train capacity of 1.6 × 106 m3 (STP)/h.
Production of LNG requires bulk removal of all
sulfur and carbon dioxide to avoid freezing in
the liquefaction units. The aMDEA process of
BASF is used to remove simultaneously hydro-
gen sulfide and carbon dioxide to the low ppm
level. Additional molecular sieve adsorbers trap
organic sulfur components such as mercaptans.
Degradation products of MDEA are sec-
ondary and primary amines, which also serve as
activator for carbon dioxide absorption. There-
fore in selective MDEA applications the carbon
dioxide absorption is often higher than expected.

Figure 51. Activated MDEA process for carbon dioxide removal with semi lean amine regenerated by flash a) High pressure
absorber; b) First flash drum; c) Second flash drum; d) Solvent heat exchanger; e) Regenerator; f) Solvent cooler; g) Amine
filter
Figure 52. aMDEA plant removing carbon dioxide from 15
000 m3 (STP)/h raw gas of a steam reformer (Courtesy of
BASF AG and Lurgi Oel Gas Chemie GmbH)
Sterically Hindered Amines. Solvents based
on sterically hindered amines are licensed by
Exxon Research and Engineering Co. under the
trade name Flexsorb [192, 193]. These sterically
hindered amines are secondary amine molecules
bearing one bulky side group. This steric hin-
drance reduces the carbamate reaction rate by
more than an order of magnitude compared to
secondary amines. The basicity of this hindered
secondary amine is higher than that of MDEA
resulting in a higher hydrogen sulfide absorption
capacity. Therefore, very high selectivity is at-
tained in absorbers with short contact time [194].
Gas Production 105
Flexsorb SE solvent is a strongly hindered
amine designed for high hydrogen sulfide selec-
tivity [195]. It is therefore best suited for gases
with high carbon dioxide: hydrogen sulfide ratio
and in applications where low carbon dioxide ab-
sorption is required, such as Claus tail-gas treat-
ing. The benefits of Flexsorb have been demon-
strated in various low pressure retrofit appli-
cations. Higher gas throughputs were achieved
with lower solvent circulation rates compared
to the original solvent. In addition the steam re-
quirement for regeneration is reduced due to the
lower solvent circulation rate.
With Flexsorb SE Plus hydrogen sulfide con-
centrations as low as 10 ppm (mL/m3 ) at atmo-
spheric absorber pressure are possible at the cost
of 25 % higher circulation rates relative to Flex-
sorb SE. Acid buffer is added to the solution,
which facilitates solvent regeneration.
Hot Potassium Carbonate Process. The
potassium carbonate process has been success-
fully applied for carbon dioxide removal since
1960. The hot potassium carbonate process (HP)
uses a potassium carbonate concentration in
aqueous solution of 20 – 40 wt %. The reaction
with carbon dioxide that occurs in the process
also shows an equilibrium behavior that is fa-
vorable to absorption even at elevated tempera-
ture. As a result of the high absorber temperature
(near the atmospheric boiling point of the solu-
tion), relatively low heat input is required for
regeneration by reboiling.
106 Gas Production
Figure 53. Typical flow diagrams of the HP process for CO2 removal
A) Single stage; B) Single stage with splitflow; C) Two stage process
Investment costs are lower than for MEA and
DEA because solvent heat exchangers are not
required. Figure 53 shows three typical versions
of the process. The single stage type (Fig. 53 A)
can be varied by cooling part of the solvent to
lower the vapor pressure of carbon dioxide so
that a higher purity of the treated gas can be ob-
tained (Fig. 53 B). A carbon dioxide content of
less than 0.5 % in the treated gas can be obtained
economically only by using a two-stage design
(Fig. 53 C).
The main application of the HP wash is re-
moval of carbon dioxide from converted reform-
ing gas, because process conditions are almost
ideal for this. The carbon dioxide partial pres-
sure after conversion is normally in the range
of 0.4 – 0.7 MPa and, therefore, in the optimum
range for equilibrium behavior of the solution
(see Fig. 42, line e). In the production of hydro-
gen and synthesis gas for ammonia, a methana-
tion stage follows as a fine purification stage for
converting carbon monoxide and carbon dioxide
residues. This step is operated at high tempera-
ture and in the presence of water, as in carbon
monoxide conversion. This is in keeping with
the high absorption temperature, as well as the
aqueous solvent basis of the HP process. In view
of the 0.25 – 0.4 % carbon monoxide in the gas
downstream of the shift conversion, the gas in the
absorption stage does not have to be cleaned to
a carbon dioxide content of less than 0.1 %. The
converted gas contains enough steam to cover
the heat requirements of the HP process.
Figure 54 shows a characteristic working di-
agram for a two-stage HP absorption process. In
addition to the equilibrium curve, which is prac-
tically identical for absorption and regeneration,
operating lines of the absorber and the regener-
ator, together with determination of the theoret-
ical stages according to McCabe – Thiele, are
shown. The slopes of the operating lines are de-
termined by the split fraction of semi-lean and
lean solvent. Optimum adjustment of the split
fraction results in the minimum number of the-
oretical stages required.
The process is available in different versions.
Modifications differ less in the basic principles
of the process than in the additives used as cor-
rosion inhibitors or activators to increase mass
transfer.
Modifications. The Benfield process uses
mainly solutions with 25 – 30 % potassium car-
bonate and vanadate as an additive. Several de-
velopments have led to its widespread commer-
cial application, especially with regard to am-
monia plants based on natural gas and naphtha
[196].
The solution used in the Catacarb process
contains proprietary additives. Amine promoters
enhance mass transfer rates and inhibit corrosion
in applications such as purification of ammonia
synthesis gas, hydrogen production, and natural
gas. If no carbon dioxide is present a solution
of potassium borate is used for hydrogen sulfide
removal instead of potassium carbonate.

Figure 54. McCabe – Thiele diagram for a two-stage HP
process
The Lurgi HP process uses borate as an ad-
ditive, which accelerates absorption and is ef-
fective as a corrosion-inhibiting compound. In
this process modification, both carbonyl and hy-
drogen sulfides can also be absorbed in the hot
potassium carbonate solution. In the high-purity
version, for example, hydrogen sulfide is re-
moved to < 1 ppm. It can be absorbed selec-
tively against carbon dioxide under certain con-
ditions because of their different reaction veloc-
ities. The selectivity, together with other proper-
ties of the HP process (high absorption temper-
ature, low investment and utility costs), is par-
ticularly advantageous for purifying coal gasifi-
cation gas to fuel gas quality. Because coal gas
usually contains additional impurities that can-
not be removed in an HP wash, a precleaning
step is required (see Section 5.4.4).
The regeneration operates under vacuum in
the Vacasulf process of Krupp Uhde. The pro-
cess is mainly applied for low pressure desul-
Gas Production 107
furization of coke oven gas. Stringent lean gas
qualities are achieved by a fine wash step with
caustic soda.
Absorption in Ammonia Solution and
Caustic Soda. Desulfurization with ammonia
solution to purify gases containing ca. 500 mg of
hydrogen sulfide per cubic meter was formerly
very common for treating coke oven gas and
is still used in some cases. However, the pro-
cess has not become established for cases with
more stringent purity requirements. On the other
hand, it is an integral part of new developments
for separating hydrogen sulfide – carbon diox-
ide and ammonia for sulfur recovery from sour
gases containing ammonia, and for recovering
ammonia from gas condensates.
Absorption of carbon dioxide and hydrogen
sulfide in caustic soda produces bicarbonate and
bisulfide the bonding of which is so strong that
the vapor pressure of the sour components prac-
tically disappears. Therefore, gas purities as low
as 0.1 mL/m3 (CO2 and H2 S) or less can be at-
tained. However, regeneration, which is possible
in principle but very complex, is dispensed with.
Caustic soda is thus used only for fine purifica-
tion.
5.4.2.3. Physical – Chemical Absorption
Processes
Processes utilizing a solvent mixture of a phys-
ical organic component and a chemically acting
component are termed physical – chemical ab-
sorption processes or mixed solvent processes.
Mixed solvents provide a higher capacity than
the pure physical solvent because of the addi-
tional chemical bonding of the acid gases with
the chemical acting constituent. Fewer stages are
normally required in the absorber due to the ac-
celeration of mass transfer by the chemical re-
action. The physically acting constituent of the
mixed solvent provides absorption capacity for
trace components such as carbonyl sulfide and
organic sulfur components, which can not be re-
moved with aqueous amines.
The best known processes are the Shell Sulfi-
nol process and the Lurgi Amisol process.
Sulfinol Process. The Sulfinol solvent is a
three-component solution containing the fol-
lowing constituents: an alkanolamine, usually
108 Gas Production
DIPA (diisopropanolamine), sulfolane (tetra-
hydrothiophene dioxide), and water. The ratio
of the constituents varies according to the re-
quirements of the application. The process, in-
troduced in 1964, was used in its early years
to remove hydrogen sulfide and carbon dioxide
from gasification gases in steam reforming, as
well as from natural gases [197]. More than 180
plants are reported to be in operation in 1998.
The process displays many properties and
advantages of both chemical and physical pro-
cesses. Acid gas loading is higher at elevated
pressure and less steam for regeneration is re-
quired compared to purely chemical solvents.
The physical character of the solvent facilitates
to achieve hydrogen sulfide concentration as low
as 1 ppm (mL/m3 ) in the purified gas. Sulfinol
is capable of removing other sulfur compounds
including mercaptans, carbonyl sulfide, and car-
bon disulfide. The process flow sheet is very sim-
ilar to chemical absorption processes (Fig. 49).
Flashing of the rich solvent is often included as
additional step to recover valuable gases and to
increase the hydrogen sulfide concentration in
the Claus gas.
The Sulfinol-M process uses MDEA instead
of DIPA as chemical constituent in the solvent.
This process can be designed for selective hydro-
gen sulfide absorption while a large percentage
of the carbon dioxide from the raw gas slips to
the treated gas.
Amisol Process. The Amisol solvent con-
sists of an alkanolamine, normally MEA or
DEA, in conjunction with methanol. This sol-
vent mixture was successfully used in the first
commercial Amisol plant in the early 1970s to
remove carbon dioxide, hydrogen sulfide, and
carbonyl sulfide from raw gas produced in a par-
tial oxidation plant handling vacuum residues
[198]. A clean gas with very low total sul-
fur content (hydrogen sulfide, carbonyl sulfide,
mercaptans) of < 0.1 mL/m3 , as required for
synthesis gas, can be obtained by the Amisol
process. Good absorption of trace components
such as hydrogen cyanide, and higher hydrocar-
bons is also achieved. Because of the low boil-
ing point of methanol, absorption and regener-
ation temperatures are not far apart; therefore,
no lean – rich solvent heat exchangers are nor-
mally required. Selective removal of both car-
bonyl and hydrogen sulfides versus carbon diox-
ide is possible by using aliphatic alkylamines
such as diisopropylamine (DIPAM) and diethyl-
amine (DETA) [199].
The Amisol process is suitable for treating
various raw gases to absorb hydrogen sulfide,
carbonyl sulfide, and carbon dioxide along with
trace contaminants or to selectively remove sul-
fur compounds versus carbon dioxide. An exam-
ple of a commercial Amisol plant using diethyl-
amine involves purification of coal gas produced
by an entrained-bed gasifier. A concept was de-
veloped for clean fuel power stations.
Flexsorb PS. The Flexsorb PS solvent is a
mixture of a moderately hindered amine, a phys-
ical solvent, and water. This solvent is primarily
suited for natural gas clean up. More than 95 %
of carbonyl sulfide and mercaptans can be re-
moved from the gas.
5.4.2.4. Comparison of Various Absorption
Processes for Hydrogen Production and
IGCC
Hydrogen Production Based on Residue
Oil Gasification (see also 7.2). Refineries re-
quire large amounts of hydrogen for hydrotreat-
ing and hydrocracking to meet stringent fuel
specifications and to process heavier opportunity
crude oils. The residues from visbreaker or hy-
drocracker units are an inexpensive feedstock for
hydrogen production by gasification. The carbon
monoxide from the raw gas is converted to hy-
drogen in a CO shift unit and the resulting raw
hydrogen must be purified from acid gases and
trace impurities. The selection of the appropri-
ate gas purification technology depends on the
required hydrogen purity, the value of the fuel
gas and CO2 byproducts, and the plant emission
regulations.
Acid gases must be removed from the raw hy-
drogen downstream of the sulfur-tolerant shift
unit. This can be achieved with various pro-
cesses.
In the first case (see Fig. 55A), the Rectisol
process produces an H2 S-rich sour gas suitable
for the Claus unit. In addition, CO2 bulk removal
is economical and a pure CO2 stream is gener-
ated which can be used for sequestration or as
industrial gas, or vented without further treat-
ment. A pressure swing adsorption (PSA) unit is

Figure 55. Gas purification options for hydrogen production from gasification of heavy residue oil
A) Rectisol-based acid gas removal and PSA for hydrogen fine purification; B) Selective acid gas removal and PSA for
hydrogen purification; C) Acid gas fine removal by Rectisol and methanation for hydrogen purification
used to free the hydrogen from impurities such
as methane, nitrogen, carbon monoxide, and ar-
gon, which are concentrated in the PSA off-gas.
The PSA off-gas is a high-BTU, low-sulfur gas,
since Rectisol removes besides H2 S also eco-
nomically virtually all the CO2 and other trace
acid components.
In the second case (see Fig. 55B) a selective
acid gas removal (AGR) process is applied such
as Purisol or Selexol, which also produces an
H2 S-rich sour gas suitable for the Claus unit.
Typically, 20–30 % of the CO2 content of the raw
gas is removed in a selective gas purification pro-
cess. This CO2 is produced as a separate, impure
CO2 stream with a significant sulfur concentra-
tion. The sulfur impurity in the CO2 stream is
normally not a problem for sequestration pur-
poses or enhanced oil recovery. Simple venting,
however, is usually not permitted.
Since AGR is selective, a considerable
amount of CO2 passes to the PSA unit in this
case and is separated there. The PSA unit also
separates the remaining sulfur impurities. Due
to the high CO2 content the PSA off-gas has
a low heating value. It also contains a signifi-
cant amount of sulfur because both Selexol and
Purisol leave traces of H2 S in the low ppm range
in the purified gas and remove carbonyl sulfide
(COS) only partly.
In the third case (see Fig. 55C), if hydrogen
production is to be maximized but high purity
is not required and additional fuel gas is of low
value, the PSA unit can be replaced by a metha-
nation reactor which converts CO and CO2 to
Gas Production 109
methane. Since all impurities end up in the prod-
uct hydrogen, the gas purification unit must re-
move all sulfur species to the ppb level and re-
move bulk CO2 to the low ppm range. Rectisol is
the process of choice for this configuration. Hy-
drogen purity exceeding 97 % can be achieved,
which is normally sufficient for hydrotreating
and hydrocracking applications, and no fuel gas
is produced. This process configuration gives the
highest specific hydrogen production.
Gas Purification for Power Production by
Combined Cycle IGCC. In an integrated gasi-
fication combined power cycle (IGCC), fuel gas
produced by partial oxidation of coal or residual
oil is used to power a gas turbine (see 7.3). A
gasification process is advantageously applied
which recovers the energy of the hot gas leav-
ing the reactor in a waste-heat boiler to produce
high-pressure steam. The heat recovered from
gasification and the exhaust gas of the gas tur-
bine are utilized for a steam cycle (see Fig. 56). If
the IGCC is installed in a refinery, additional hy-
drogen can easily be produced. Part of the desul-
furized gas downstream of the acid gas removal
is passed to a CO shift unit and the hydrogen is
purified in a PSA unit.
Due to mechanical restrictions gas turbines
usually operate at pressures below 30 bar,
whereas gasification and gas cleaning oper-
ate advantageously at pressures above 50 bar.
Higher operating pressures have the benefit of
smaller equipment size. Additionally the in-
creased solubility of the sulfur compounds in the
110 Gas Production

Figure 56. Cogeneration of power (IGCC) and hydrogen WHB-waste-heat boiler, AGR-acid gas removal, HRSG-heat recovery
steam generation, PSA-pressure swing adsorption, MARS-metal/ash recovery system

absorbing solvent at higher pressure results in a
lower solvent circulation rate that reduces utility
demand for regeneration and solvent cooling.
The pressure difference between gasification
and gas turbine can be utilized for additional
power generation efficiency of the IGCC from
45.4 to 46.2 %.
Table 29. Comparison of low pressure IGCC and high pressure
IGCC with gas expansion

power generation by expansion of the purified High pressure gas Low pressure gas
cleaning with cleaning
gas downstream of gas cleaning in a gas ex- expansion
pander (see Fig57c). During expansion with Gasifier pressure 58 bar 24 bar
power generation the gas temperature is reduced Gas turbine pressure 22 bar 22 bar
Utility consumption
considerably. The expanded cold gas can be used Cooling water for gas 180 m3 /h 1230 m3 /h
for solvent cooling (d). The Rectisol process can cleaning
be advantageously used for fuel gas production Steam for regeneration 8.6 t/h 13 t/h
due to its ability to remove all sulfur compo- Electrical power for gas − 0.4 MW 8.1 MW
cleaning
nents, including carbonyl sulfide. The required Electrical power for air 32.6 MW 29.1 MW
cooling to low temperatures can be done com- separation
pletely by the cold gas downstream of the expan- Total electrical power 32.2 MW 37.2 MW
Capital expenditures (relative)
sion, if the pressure difference between gasifica- Gas cleaning unit 117 100
tion and gas turbine is high enough. Complete IGCC plant 102 100
A comparison of a process with low-pressure Efficiency of electrical power generation
Overall efficiency 46.2 % 45.4 %
gasification, gas purification, and gas turbine and
a process with high-pressure gasification and gas
cleaning, gas expansion, and low-pressure gas An off-gas-free selective desulfurization for
turbine is compiled in Table 29. The calculation fuel gas production within an IGCC applying
is based on a residual oil gasification of 100 t/h a selective absorption process such as Selexol
and a net electrical power generation of 500 MW. and Purisol is shown in Figure 58. This process
Capital expenditures only for the gas cleaning configuration operates successfully in an IGCC
unit are increased by 17 % by the gas expansion plant in Italy based on heavy residue gasifica-
equipment, but for the complete IGCC plant the tion. Undesired trace components of the gasifi-
capital expenditures are increased only by 2 %. cation such as cyanides or higher hydrocarbons
The utility demand is decreased by 13 %, and are removed in a prewash stage (a). The rich sol-
this leads to an overall increase of the electrical vent of the main wash is flashed in the reabsorp-
 Gas Production 111

Figure 57. Rectisol for integrated gasification combined power cycle (IGCC) with gas expansion a) Crude gas cooling;
b) H2 S absorber; c) Gas expansion turbines; d) Solvent cooling by expanded gas; e) Solvent cooling by refrigerant, f) Flash
regeneration, g) Hot regeneration

Figure 58. Off-gas free Purisol process for selective hydrogen sulfide removal in an integrated combined power cycle (IGCC)
a) Prewash section, b) H2 S absorber, c) Reabsorber, d) Flash regeneration, e) Hot regeneration, f) Claus tail gas recycle blower,
g) Fuel gas recycle compressor (optional)

tion column (c). Carbon dioxide and valuable
components are recovered as fuel gas, whereas
hydrogen sulfide is reabsorbed in the solvent in
order to increase the hydrogen sulfide concen-
tration in the sour gas to the Claus unit. The
fuel gas leaving the reabsorption column over-
head can either be recompressed and added to
the high-pressure purified gas or can be used
as low-pressure fuel gas for the steam boiler of
the IGCC. The typical sulfur recovery rate of a
two-stage Claus unit is 95 - 96 %. The off-gas
of the Claus unit contains beside unconverted
hydrogen sulfide considerable amounts of SO2
and COS, which are converted to hydrogen sul-
fide in a catalytic hydrogenation step. The hy-
drogenated off-gas is compressed and fed to the
reabsorption step of the acid gas removal unit.
So-called zero-emission IGCC (Fig. 59) is
discussed in view of the Kyoto protocol for re-
ducing carbon dioxide emissions. In addition to
total sulfur removal, carbon from the feedstock
is also captured and concentrated in a second
pure carbon dioxide product stream. The fuel
gas to the gas turbine is pure hydrogen. The
gasification process converts the carbon of the
feedstock mainly to carbon monoxide, which is
further converted to carbon dioxide and hydro-
gen in a carbon monoxide conversion unit (→
5.1). The carbon dioxide can easily be separated
from the hydrogen in the absorption process and
112 Gas Production
Figure 59. “Zero-emission” IGCC concept WHB-waste-heat boiler, AGR-acid gas removal, HRSG-heat recovery steam
generation, PSA-pressure swing adsorption, MARS-metal/ash recovery system
a pure carbon dioxide stream is produced, which
can be used for industrial purposes such as urea
production, for enhanced oil recovery, or can be
sequestered for carbon dioxide emission control.
The economically achievable carbon recovery
rate and the purity of the carbon dioxide product
stream depend on the selected absorption pro-
cess. The Rectisol process allows the production
of ultralow-sulfur fuel gas (hydrogen) to the gas
turbine and generation of very pure carbon diox-
ide. Selective-solvent processes such as Selexol
and Purisol leave more sulfur in the fuel hydro-
gen. As expressed by the designation selective,
this type of solvent requires greater effort for re-
moval of bulk carbon dioxide. In addition, the
carbon dioxide product stream contains larger
amounts of hydrogen sulfide. Chemical absorp-
tion processes are not particularly suitable for
removing these large amounts of carbon diox-
ide due to the large amount of steam required
for solvent regeneration.
5.4.3. Liquid-Phase Oxidation Processes
In liquid phase oxidation processes hydrogen
sulfide is absorbed from a gas stream in a liquid
solution and directly oxidized to sulfur in the so-
lution. The overall reaction can be expressed as
follows:
H2 S+1/2 O2 → S+H2 O
The oxidizing agent in the solvent is reduced
and solid sulfur is formed in the gas liquid con-
tactor. In the subsequent regeneration step the
solution is oxidized with air converting the oxi-
dant to its oxidized state.
The main process steps are shown in Figure
60. The feed gas is contacted with the redox solu-
tion in a suitable gas – liquid contactor such as
a countercurrent packed bed absorber, a spray
tower, a cocurrent sparged tower, or a venturi
scrubber. The sulfur formation takes place in the
absorber and is completed in a downstream reac-
tion vessel which may also serve as gas – liquid
separator if the absorber works in the cocurrent
mode. In the oxidizer the active component is
converted from the reduced to the oxidized state
and the sulfur particles are separated either as
froth by flotation or as slurry by settling. The
regenerated solution is recycled to the gas – liq-
uid contactor. The sulfur froth or slurry is either
separated in a filter unit or a sulfur melter.
Liquid-phase oxidation processes are espe-
cially suitable for selective removal of hydrogen
sulfide versus carbon dioxide, because carbon
dioxide does not react with the redox solution.
Essentially complete hydrogen sulfide removal
with concentrations below 1 ppm (mL/m3 ) in the
treated gas is attainable. Contrary to physical or
chemical absorption processes in which the off-
gas of the regenerator must be generally treated

Figure 60. Schematic flow diagram of liquid phase oxidation processes
in an additional unit to produce sulfur or sulfu-
ric acid, in liquid-phase oxidation processes the
formation of elemental sulfur occurs within the
purification unit itself.
The main applications of liquid-phase oxida-
tion processes are
1) Desulfurization of coke oven gas, natural gas,
and synthesis gas with low hydrogen sulfide
concentration,
2) Treatment of gases that cannot be processed
economically in a Claus plant (e.g., due to
low hydrogen sulfide concentration, small to-
tal amount of sulfur),
3) Treatment of Claus tail gases,
4) Replacement of dry purification processes,
and
5) Treatment of very low raw gas rates (e.g.,
landfill gas).
Economical operation is limited to sulfur pro-
duction rates less than 20 t/d due to high utility
costs. Continuous solvent make-up is required
because the solvent is susceptible to chemical
and thermal degradation and because of losses
with the sulfur filter cake. Continuous solvent
purging is required due to the accumulation of
side products such as thiosulfate in the solvent
circulation. Thiosulfate production can be kept
below 1 % of the hydrogen sulfide converted, if
operating conditions such as temperature and so-
lution pH are carefully controlled. A buffering
agent in the solution avoids large pH swings due
to carbon dioxide absorption.
Carbonyl sulfide and organic sulfur compo-
nents are only partly removed in liquid oxidation
processes. Hydrogen cyanide and sulfur dioxide
Gas Production 113
are almost quantitatively absorbed and react to
thiocyanate and sulfate in the solution. These
salts accumulate in the circulating liquor and in-
crease the required purge stream and the amount
of hazardous waste byproducts generated. Am-
monia is also absorbed and causes pH changes.
Ammonium polysulfide is formed with solid sul-
fur, increasing the salt concentration in the so-
lution. Ammonia is stripped in the oxidizer and
may cause odor problems in the vent stream.
Sulfur quality is often not crucial because of
the small amount of sulfur produced. Residual
solvent impurities have to be removed from the
filter cake by washing with demineralized water.
An additional sulfur washing and melting step
is required to achieve sulfur quality similar to
Claus plant sulfur.
A drawback of all liquid-phase oxidation pro-
cesses is the relatively low oxidation capacity of
the solution for hydrogen sulfide. This necessi-
tates large solvent circulation rates. The heat of
reaction generated by the oxidation of hydrogen
sulfide must be dissipated at low temperature
and cannot be used, as in the Claus process, to
generate valuable steam. Only part of the heat
of reaction can be used for the heat demand of
the process.
The development of liquid phase oxidation
processes started with iron oxide suspended in
aqueous alkaline solutions (e.g., Ferrox, Gluud,
and Manchester). The second generation of
processes applied thioarsenate (e.g., Thylox,
Giammarco–Vetrocoke [200]). They have lost
market acceptance because of the toxicity of
the solution. An aqueous mixture of vanadium
pentoxide, naphthoquinone, and alkali carbon-
114 Gas Production
ate is the basis of the widely used Stretford pro-
cess [201], the Takahax process [202] and the
Sulfolin process. Presently, environmental con-
cerns about the vanadium content in the purge
stream have resulted in the selection of iron
chelate-based processes such as Lo-Cat [203],
SulFerox [204] and Sulfint [205] for most ap-
plications. Processes using sulfur dioxide are
Townsend [206] and IFP Clauspol [207]. In the
end they have not been commercially successful.
A new class of processes apply microorganisms
to convert hydrogen sulfide to sulfur (e.g., Shell-
Thiopaq [208] and Bio-SR).
Vanadium-Based Solutions. The Stretford
process, originally developed for the removal of
hydrogen sulfide from coke oven gas, has proved
to be equally suitable for desulfurization of other
gas streams such as natural, synthesis, and tail
gases.
The Stretford process uses an aqueous solu-
tion containing sodium carbonate, sodium bicar-
bonate, anthraquinonedisulfonic acid (ADA),
and sodium metavanadate. The process can be
considered to proceed in the following steps:
1) Absorption of hydrogen sulfide in the alkali
solution,
H2 S+Na2 CO3 → NaHS+NaHCO3
2) Oxidation of hydrogen sulfide to sulfur by
sodium metavanadate,
4 NaVO3 +2 NaHS+H2 O → Na2 V4 O9 +2 S
+4 NaOH
3) Reoxidation of the reduced vanadate by ADA
Na2 V4 O9 +2 NaOH+H2 O+2 ADA →4 NaVO3
+2 ADA (reduced)
4) Oxidation of reduced ADA by air in the re-
generator
2 ADA (reduced) +O2 → 2 ADA+2 H2 O
Figure 61 shows a simplified flow diagram
of the Stretford process for selective desulfur-
ization. The raw gas is brought in contact coun-
tercurrently with the solution in the absorber (a)
and purified to a level of < 1 ppm of hydrogen
sulfide. The solution flows from the absorber
bottom to the reaction vessel (c) to complete the
conversion of hydrogen sulfide to elemental sul-
fur; then the solution is regenerated in the oxi-
dizer (d) by contact with air.
Sulfur is separated by flotation and removed
at the top of the oxidizer (d) as froth containing
5 – 10 % solids. The sulfur froth is collected in
a vessel and subsequently processed in a filter
or centrifuge. The sulfur has to be washed with
water to separate solution and sulfur and to pro-
duce relatively pure sulfur. Though installed in
numerous commercial plants, the Stretford pro-
cess suffers from the drawbacks of formation
of byproducts and environmental concern about
vanadium in the effluent streams.
In the solvent used in the Sulfolin process
ADA is replaced by an organic nitrogen vana-
dium promoter [209]. Like the Sulfolin process
the Unisulf process [210] claims a reduced for-
mation of byproducts and lower corrosivity, re-
sulting in lower chemical consumption.
Iron-based Solutions. Iron is kept in the
aqueous solution by organic ligands or chelat-
ing agents (L). The basic chemistry in the iron
chelate solution can be summarized as follows:
Absorption:
2 Fe3+ L+H2 S → 2 Fe2+ L+S+2 H+
Regeneration:
2 Fe2+ L+1/2 O2 +2 H+ → 2 Fe3+ L+H2 O
In iron chelate processes sulfur is generally
separated by settling. The slurry containing 10 –
15 wt % sulfur is further processed by filtration
in order to recover the solvent. Stainless steel
equipment is required due to the high solvent
power of the solution for iron.
The Lo-Cat process is licensed by U.S. Filter.
The flow sheet of the conventional Lo-Cat pro-
cess is similar to the SulFerox process shown
in Figure 63. Oxidation of the rich solvent and
sulfur settling take place in the same vessel. The
solution contains up to 0.3 wt % iron resulting in
large solvent circulation rates with high power
demand for solvent pumping especially in high
pressure gas purification.
In the Lo-Cat autocirculation design, hydro-
gen sulfide absorption, the conversion to sul-
fur, and the oxidation of the redox solution take
place in one vessel in separate compartments
(Fig. 62). The autocirculation design is appli-
cable for low pressure gases such as acid gases
from amine units and Claus tail gases. Due to the
compact design hydrogen sulfide is not totally

Figure 61. Schematic of a Stretford plant for selective H2 S removal
a) Absorber; b) Air compressor; c) Reaction vessel; d) Oxidizer; e) Solvent vessel; f) Sulfur filter
converted to sulfur before the solution is con-
tacted with air. This causes an increase in the
thiosulfate formation of up to 5 % of the con-
verted hydrogen sulfide.
Figure 62. Lo-Cat autocirculation design
The Lo-Cat process operates with the stoi-
chiometric ratio of iron(III): hydrogen sulfide of
2: 1. In the Lo-Cat II process the ratio of iron(III)
to hydrogen sulfide is maintained at 1: 1. An im-
proved solution chemistry enhances the reaction
kinetics. The rich solvent from the absorber is
mixed with oxidized solution upstream of the
oxidizer. Residual HS− in the rich solvent is
thus totally converted to sulfur by iron(III) be-
fore the solution is contacted with oxygen result-
ing in thiosulfate formation below 1 %. Due to
Gas Production 115
the substoichiometric operation less solvent has
to be circulated to the high pressure absorber, re-
ducing the power requirement for pumping. The
Lo-Cat II process is also available in the auto-
circulation design.
The SulFerox process was developed by Shell
and is licensed by DOW and Shell (Fig. 63).
Special feature of this process is the high iron
concentration of 2 to 4 wt %, reducing equip-
ment sizes and pumping costs. The high iron
concentration accelerates the reaction kinetics
and thus the hydrogen sulfide absorption rate.
One possible design for the absorption section
is the patented cocurrent pipeline contactor with
proprietary mixing elements which makes use
of the fast reaction kinetics. Low pressure drop,
nearly infinite hydrogen sulfide turndown capa-
bility, and low fouling tendencies are provided
in a small diameter vessel. Due to the fast re-
action kinetics all of the hydrogen sulfide ab-
sorbed is converted to sulfur and no HS− ions
are present in the rich solution when entering the
oxidizer. Thiosulfate formation is claimed to be
below 0.1 %.
The pH of the SulFerox solution is kept be-
low 8. Carbon dioxide solubility in the SulFerox
solution is therefore similar to that in water, re-
sulting in a very high hydrogen sulfide selec-
tivity. The SulFerox solution is also capable of
removing about 70 % of mercaptans present in
the raw gas.
A comparison between one of the amine pro-
cesses plus Claus plant, autocirculation Lo-Cat,
direct Lo-Cat, Lo-Cat II, and the SulFerox pro-
116 Gas Production
Figure 63. Schematic flow diagram of the SulFerox process. A) Absorber, b) Gas-liquid separator, c) Flash drum, d) oxidizer,
e) Sulfur settling vessel, f) Sulfur filter (Courtesy of Shell International Oil Products B.V.)
cess in technical and economical terms was per-
formed by the Gas Research Institute (GRI)
[213]. Lo-Cat II and SulFerox perform very sim-
ilar for the two high pressure gas cleaning cases
studied. The two Lo-Cat modifications and an
amine process plus Claus plant result in signifi-
cantly higher sulfur production costs.
Biological Processes. Suitable bacteria con-
vert hydrogen sulfide under certain conditions to
sulfur. The processes consist of the same process
steps as conventional liquid phase oxidation pro-
cesses (Fig. 60). In the Shell-Thiopaq process
hydrogen sulfide is absorbed into an iron-free
caustic solution. The dissolved sulfide is sub-
sequently oxidized to sulfur in the Thiopaq re-
actor by bacteria of the genus Thiobacillus. The
Bio-SR process of NKK Corporation uses a non-
chelated iron(III) sulfate solution. The bacteria
act as catalyst in the oxidizer to enhance the ki-
netic of regeneration from iron(II) to iron(III)
sulfate. Both processes have demonstrated to
be capable for removing hydrogen sulfide from
high pressure natural gases.
5.4.4. Removal of Gas Impurities of Low
Concentration
Raw gases contain numerous gaseous impurities
besides the acid gases. High boiling hydrocar-
bons have to be removed because of dew point
specifications in the purified gas. Organic sulfur
compounds are harmful to most catalysts. Unsat-
urated hydrocarbons tend to polymerize in the
solvent circulation. Acids, hydrogen cyanide,
and ammonia tend to form salts in the absorption
solution. Gases from residual oil or coal gasifi-
cation often contain volatile metal compounds
such as mercury and metal carbonyls.
The absorption of impurities depends on the
solvent. Higher hydrocarbons will only be part-
ly absorbed in water-based amine solvents and
cause foaming problems. Low-boiling impuri-
ties are trapped in organic solvents such as Se-
lexol and Purisol and can not be removed by
solvent stripping. Rectisol has the advantage that
the impurities absorbed are purged together with
the process water from the solvent loop. Al-
though the concentration of impurities in the gas
is often in the ppm range they may accumulate in
the solvent circulation to levels that cause prob-
lems such as fouling, foaming, corrosion, and
solvent degradation. Therefore they are often re-
moved in a separate prewash process upstream
of the acid gas removal.
Water Wash Process. Even a simple water
prewash can remove acids, cyanide compounds,
and ammonia very effectively from the gas, be-
cause their water solubility (e.g., expressed by
the absorption coefficient) is very high (see Fig.
64).
However, high solubility also means difficult
regeneration, especially because purity require-
ments of wastewater are stringent and fresh wa-
ter is scarce. Therefore, the laden water must of-
ten undergo complex stripping with steam and
impurities must then be incinerated.

Figure 64. Solubility of different gases in water at low
pressure 0.1 MPa
Oil Wash Process. Hydrocarbons, espe-
cially the normally undesirable unsaturated ones
that tend to polymerize, as well as saturated
high-boiling ones, are best removed by using an
oil wash, which generally is designed with a hot
regeneration stage (see Fig. 41 C). Occasionally,
the vapor pressure of the washing agent in the
absorber is too high so that a higher boiling oil
fraction must be used. If the boiling temperature
of this fraction is too high, it cannot be boiled
indirectly in the regenerator with steam but only
directly with live steam or a fired reboiler.
In some types of raw gas — especially that
generated from coal — removal of the main gas
impurities can require a whole series of pre-
wash steps before highly concentrated gas com-
ponents such as carbon dioxide are separated and
chemically converted. Examples are prewashes
with water for hydrogen cyanide and ammonia,
followed by absorption of hydrogen sulfide in
Gas Production 117
aqueous ammonia. In a final fine wash step ben-
zene, naphthalene, gum formers, and other un-
saturated hydrocarbons are absorbed in an oil
wash.
Rectisol Prewash. The previously described
prewash systems were particularly important for
raw gas produced from coal pressure gasifica-
tion, which contained almost all the impurities
named, extending to gas naphtha. Therefore, at-
tempts were made to find a simpler solution to
this problem, which succeeded in conjunction
with the development of the Rectisol process:
all impurities are removed with only one solvent,
methanol, which is also used downstream for re-
moval of hydrogen sulfide and carbon dioxide.
Figure 65 shows a simplified scheme of such
a prewash in which only a small quantity of cold
methanol removes water, hydrogen cyanide, am-
monia, gum formers, gas naphtha, and other im-
purities from the raw gas. Methanol is regen-
erated by extraction with water and two-stage
distillation.
Condensation. Low boiling substances and
water have to be removed from natural gases
to meet pipeline dew point specification. This is
often accomplished by condensation at low tem-
perature. The Ifpexol process (Fig. 66) of Institut
Français du Petrol (IFP) removes water and re-
covers liquid hydrocarbons from raw natural gas
[211]. Part of the raw gas is brought into con-
tact with a methanol rich stream in the methanol
stripper (a). The methanol concentration in the
water leaving the stripper as bottom product can
be reduced to 50 mg/kg. The methanol vapor in
the overhead raw gas prevents hydrate and ice
formation in the gas chiller (b). The liquid con-
densate is separated in a settler vessel (d) into the
liquid hydrocarbon fraction and the methanol –
water fraction. The methanol – water fraction is
recycled to the methanol stripper. The pretreated
gas can be further purified by any suitable pro-
cess.
Mercury Removal. Mercury emissions
from coal-based power plants are of environ-
mental concern. Conventional coal-fired power
stations have to treat a huge volume of flue gas
in an activated-carbon adsorber. Power produc-
tion based on coal gasification (IGCC) allows
easier removal of mercury. The Rectisol process
118 Gas Production

Figure 65. Rectisol prewash for raw gas from coal

a) Extraction system; b) Azeotropic distillation column; c) Methanol – water distillation column

Figure 66. Gas pretreating by condensation with Ifpexol process. a) Methanol stripper, b) Gas chiller, c) Gas – liquid separator,
d) Liquid – liquid separator

for acid gas removal also traps mercury with
no additional adsorption step required. Other
absorption processes require an additional acti-
vated carbon guard bed, which has to treat the
smaller amount of fuel gas to the gas turbine.
5.5. Adsorption Processes
5.5.1. Fundamentals (→ Adsorption)
Three types of adsorbents are particularly suit-
able for the adsorption of gaseous components
in fixed beds on an industrial scale:

1) activated aluminum oxide or silica gel,
2) molecular sieves, and
3) activated carbon.
Apart from process conditions such as pres-
sure and temperature, the degree of adsorp-
tion on the above-mentioned solids is deter-
mined also by the structure of the adsorbent and
the properties of gaseous components, such as
volatility and polarity. Adsorption of substances
that are characterized by high volatility and low
polarity — typical examples are hydrogen and
helium — is very poor or almost imperceptible,
whereas water and carbon dioxide, for example,
are well adsorbed because of their low volatility
and high polarity. If process conditions are near
the dew point of a gas component, that compo-
nent is adsorbed preferentially.
Adsorption Mechanisms. The qualities of
adsorbents are attributable in part to their char-
acteristic material structures. Activated carbon
(→ Carbon, Chap. 5), for instance, traps and re-
tains gas molecules in minute pores measuring
only a few molecular diameters.
In addition to this minipore effect, water
molecules are adsorbed on silica gel or activated
aluminum oxide in the form of water of crystal-
lization, filling vacancies in the crystal lattice. In
the case of molecular sieves (→ Zeolites), elec-
trostatic forces come into play in addition to the
minipores and surface-enlarging micropores, in-
creasing their adsorption capacity, especially for
polar and polarizable gases.
Adsorption Conditions. A look at adsorp-
tion processes in the molecular range suggests
that these effects are improved by increasing
process pressure and decreasing temperature.
For a particular gas and a selected adsorbent,
adsorption capacity B is shown in Figure 67 as a
function of pressure p at varying temperature T.
This group of curves, which is characteristic of
each adsorbate and adsorbent, cannot be calcu-
lated quantitatively but must be determined by
empirical means.
Basic Modes of Operation in Adsorbent
Beds. Figure 67 also shows the basic modes
of operation possible for a fixed-bed adsorber.
Three possibilities exist:
Gas Production 119
Figure 67. Adsorption capacity B of adsorbents as a
function of pressure and temperature
First Basic Mode of Operation: Path 1 – 2.
At T 0 and p0 , the adsorbent is loaded to the de-
gree B1 . If the temperature T 0 is kept constant
and the pressure is increased from p0 to p1 , the
adsorbent can collect the higher load B2 . The
difference B2 – B1 is the adsorption capacity,
which can be used for pressure-swing adsorp-
tion (PSA).
Second Basic Mode of Operation: Path 3 –
4. While the pressure is kept constant at p1 , the
temperature is reduced from T 2 to T 14 . This op-
eration forms the basis of a temperature-swing
adsorption (TSA) process.
Third Basic Mode of Operation: Path 4 – 5.
This classic method of adsorption and regenera-
tion uses the low temperature T 1 and high pres-
sure p1 for adsorption, and then regenerates the
system by decreasing the pressure to p0 and in-
creasing the temperature to T 2 by heating. The
adsorption capacity, described by the difference
B4 – B5 , is clearly the highest of the three cases.
Possible Applications. For gas condition-
ing, the adsorption of gases on fixed beds has
three possible applications:
1) elimination of undesirable trace impurities
from gas mixtures,
2) removal of contaminating gaseous compo-
nents to yield a highly pure finished product,
and
3) separation of substances.
120 Gas Production
Industrially useful applications can be derived
only from an appropriate combination of gas
components to be adsorbed and effective adsor-
bents. The following text describes a few typical
processes used in practice.
5.5.2. The “Classic” Method
The classic method (third mode of application,
above) may be illustrated by means of the re-
moval of water and carbon dioxide traces.
If gas mixtures such as hydrogen – car-
bon monoxide, hydrogen – methane, nitrogen –
methane, or air are separated into their individ-
ual components in cryogenic processes, traces
of water and carbon dioxide will lead to icing
and clogging of equipment. For this reason, such
substances must be removed completely from
the gas mixture at ambient temperature.
High carbon dioxide contents in the gas mix-
ture are normally reduced by chemical or phys-
ical wash processes (see Section 5.4) to a level
determined by the optimum arrangement of the
wash process with a view to efficient subsequent
adsorption.
The moisture content of the gas — as shown
in the example in Figure 68 — can be signifi-
cantly decreased by lowering the temperature
to near the freezing point (ca. + 5 ◦ C). The wa-
ter and carbon dioxide traces remaining in the
gas mixture can then be adsorbed efficiently and
completely on a fixed bed.
Process Description. As shown in Figure 68,
most carbon dioxide is removed from the gas
mixture in a carbon dioxide scrubber, and the
gas is cooled to ca. +5 ◦ C. Condensed water is
then removed in a downstream gas separator.
Loading Period. The gas mixture containing
a residual quantity of 100 – 150 ppm of carbon
dioxide and water is fed to adsorber (a), flowing
through it from bottom to top. For water adsorp-
tion, adsorbers (a) and (b) may be filled with ac-
tivated aluminum oxide, silica gel, or molecular
sieves. The latter have been found most effec-
tive for adsorbing carbon dioxide. After carbon
dioxide and water have been removed, the gas is
fed to the cryogenic section.
Partial Regeneration by Flashing. At the
same time, the pressurized adsorber (b) is iso-
lated from the gas flow at working temperature
and depressurized to regeneration pressure. The
gas in the adsorber is lost to the process. Ad-
sorbed water and carbon dioxide, which are lib-
erated from the adsorbent as the system is de-
pressurized, are removed from the adsorption
bed by the regeneration gas flowing in the oppo-
site direction to the gas flow during adsorption.
Fine Regeneration by Reheating. To com-
plete regeneration, the adsorber bed is purged
with hot regeneration gas containing neither wa-
ter nor carbon dioxide. In the process, the ad-
sorbent is heated to ca. 250 – 300 ◦ C. It is then
recooled with cold regeneration gas in the final
stage. Regenerated adsorber (b) is pressurized
again with clean process gas and can be used for
another adsorption cycle.
Changeover. When adsorber (a) has been
fully loaded, the gas flow is switched to adsorber
(b) while adsorber (a) is regenerated.
Process Conditions. The gas composition
and the length of the adsorption – regeneration
cycles determine the size of the adsorption unit.
The following conditions in particular must be
met: (1) The total quantity of impurities in the
gas mixture must not be too large so that the
adsorbent volume — and, along with it, the size
of the adsorbers — as well as the recycled re-
generation gas rate are kept within reasonable
limits. (2) The adsorbent quantity must be ad-
equate for the adsorption stage to ensure that
the heating and cooling time is sufficient for the
required amount of regeneration gas during the
simultaneous regeneration stage. With this ar-
rangement, the adsorption and regeneration cy-
cles normally require 4, 6, or 8 h.
Other Applications of the Classic Adsor-
ber Loop. The system is also used to adsorb
traces of water from gases before they are sent
through pipeline systems. Moisture is an unde-
sirable ballast, leading to corrosion along with
carbon dioxide, hydrate formation with meth-
ane, and freezing when cooled. The maximum
allowable moisture content, normally specified
for water dew points from −5 to −30 ◦ C, can
be achieved for small or moderate gas flow rates
at reasonable cost with adsorber units that use
activated aluminum oxide, silica gel, or molec-
ular sieves in long adsorption cycles, as well as
the classic method of regeneration. Natural or
town gas may be dried in this way before be-
ing fed to the gas grid. Similarly, adsorbers are

Figure 68. Reversible adsorber unit to eliminate residual carbon dioxide and water
a) Adsorber; b) Adsorber; c) CO2 scrubber; d) Chiller; e) Gas separator; f) Cooler; g) Heater; h) Regenerator gas; i) Cryogenic
process
used to adjust the residual moisture content of
the control air, instrument air, and compressed
air used in plants to a dew point normally of −25
to −30 ◦ C.
5.5.3. Pressure-Swing Adsorption (→
Adsorption, Chap. 7.2)
The principle of the PSA process can be illus-
trated by the recovery of highly pure hydro-
gen. If a gas mixture containing hydrogen passes
through a bed of molecular sieves at elevated
pressure and ambient temperature, these sieves
preferentially adsorb the high-density and polar
gas components. Hydrogen, being the compo-
nent least amenable to adsorption, remains alone
in the gas phase, provided the adsorber bed is
large enough for the gas rate flowing through it.
Process Description. At least two adsorbers
are required to ensure continuous production of
highly pure hydrogen. While one adsorber is in
the adsorption stage, the other is regenerated by
depressurization.
To purge the adsorbent bed, the flashed gases
are discharged from the bed in the opposite di-
rection to the flow during the adsorption stage. In
this way, the pure gas released toward the end of
the regeneration stage expels from the adsorber
those components that are adsorbed first during
the adsorption stage. The regenerated adsorbent
bed is repressurized with pure product gas or
Gas Production 121
with the gas mixture to prepare it for the next
adsorption stage.
Process Conditions. Depressurizing and re-
pressurizing adsorbers requires less time than
heating and cooling the adsorbent bed during
classic regeneration. Therefore, keeping the ad-
sorber mass, and hence also the vessels, small
by using short adsorption – regeneration cycles
is cost-effective. Cycles between 5 and 10 min
are efficient in practical applications. However,
a drawback of the process is that one vessel vol-
ume of recoverable hydrogen is lost during each
regeneration phase when the adsorber is flashed.
This is why yields of highly pure hydrogen are
generally poor relative to the recoverable hydro-
gen content of the gas mixture.
Special Process Loops. To improve the
yield, the number of adsorbers may be increased
from two to four, six, or ten.
In principle, these adsorbers or adsorber
groups simultaneously operate in the following
four modes (→ Adsorption):
1) adsorption in the first adsorber,
2) depressurizing the second adsorber,
3) purging the third adsorber at low pressure, and
4) pressurizing the fourth adsorber.
With this loop, losses of recoverable hydrogen
are reduced by using the gas released when the
second adsorber is depressurized to repressurize
the fourth adsorber to medium pressure.
122 Gas Production
Product Purity. A four-adsorber loop can
yield hydrogen of 99.999 % purity and produces
a uniform product flow, achieving yields as high
as 72 – 78 % of the hydrogen in the gas mixture.
The types and quantities of contaminants in the
gas mixture influence the size of the adsorber
beds and, to a certain extent, the yields. How-
ever, they do not influence the function of the
pressure-swing adsorption unit or the purity of
the recovered hydrogen. Contaminants are dis-
charged at ambient pressure together with the
hydrogen used for purging. In the last ten years,
this process has been used in several plants de-
signed for an output up to 100 000 m3 (STP)/h
of highly pure hydrogen.
Multicomponent Separation [214]. Fur-
ther developments of current adsorption pro-
cesses aim, on the one hand, at improving the
adsorbents and optimizing process loops and ad-
sorption – regeneration cycles and, on the other,
at utilizing various desorption effects depending
on the respective components. In the past, ad-
sorption processes were tailored to recover one
product in a highly pure form (e.g., H2 from gas
mixtures, O2 or N2 from air). Modern develop-
ments take advantage of the different properties
of individual components during desorption to
increase the content of certain components in
the outgoing flows. To this end, the origin of the
desorption flash gas is considered, for example,
raw gas from the inactive volume of the vessel
and the intergranular volume, raw gas from the
pore volume, and desorbed gas from the inner
surfaces of the adsorbent at various desorption
pressures (medium pressure, normal pressure,
vacuum). The upgrading effect is reinforced by
suitable process arrangements during desorption
(e.g., cocurrent or countercurrent desorption), in
combination with the passing of adsorbed gases
to other adsorbent beds.
This process arrangement can be used suc-
cessfully to separate gas mixtures consisting of
hydrogen, carbon monoxide, and carbon diox-
ide into highly pure product hydrogen, a carbon
monoxide fraction, and a residual gas fraction
with an increased carbon dioxide content. Anal-
ogously, a mixture consisting of nitrogen, meth-
ane, and carbon dioxide can be separated into ni-
trogen waste gas, a high-methane fraction, and a
carbon dioxide fraction. In both cases, the com-
ponents participating in the process behave very
differently because of their properties, not only
during individual adsorption cycles but also dur-
ing desorption cycles.
5.5.4. Adsorption on Activated Carbon
Activated carbon (→ Carbon, Chap. 5) shows a
strong adsorptive effect because of its extensive
pore system. Suitable preparation of carbona-
ceous materials can produce different pore struc-
tures, so that the distribution of pore radii may
be matched to specific adsorption requirements.
A variety of pore sizes down to micropores and
minipores with diameters on the order of small
gas molecules can be produced.
Applications. For gas purification, adsorp-
tion on activated carbon is used to protect down-
stream process stages or systems from traces
of compressor lubrication oil or other low-
volatility hydrocarbons, such as toluene and
washing oil, which may have entered the gas
flow through a special wash process. These ad-
sorbers are characterized by high adsorptivity,
especially for substances that are near their dew
point or have been entrained with the gas flow
in the form of minute condensate droplets. Acti-
vated carbon adsorbers can usually be regener-
ated by heating them and simultaneously purg-
ing the adsorbent bed with hot steam. Coking of
the adsorbent, however, cannot be avoided en-
tirely, so that the adsorption capacity of the ac-
tivated carbon adsorber decreases with each re-
generation cycle. Frequently, greater economy
results from providing a single activated car-
bon bed of sufficient size, operating it to break-
through, and refilling it with fresh activated car-
bon during a brief shutdown.
5.6. Cryogenic Processes (→ Cryogenic
Technology)
Cryogenic processes are used to recover pure
gas fractions from gas mixtures. Typical exam-
ples are carbon monoxide and hydrogen. The re-
quired purity of both products depends on their
intended use. The accompanying substances and
contaminants are more or less the same in all
cases: hydrogen, carbon monoxide, carbon diox-
ide, residual methane, nitrogen, oxygen, argon,

steam, contaminants such as oils, saturated and
unsaturated higher hydrocarbons, sulfur com-
pounds, nitrogen oxides, and acetylene. Their
concentrations vary according to the method
used to produce the synthesis gas. Because the
gas mixture is further processed, admixtures
such as hydrogen or carbon monoxide, carbon
dioxide or steam may lead to undesirable sec-
ondary reactions. Especially when unused gases
are recycled to the process, nitrogen, argon and
methane will lead to a build-up of inert com-
ponents and thus impair the process conditions.
Contaminants especially in the ppm range such
as sulfur compounds, steam and acetylene, but
also carbon monoxide in hydrogen, frequently
poison the catalyst or produce secondary reac-
tions at the catalyst.
In practice, a carbon monoxide product gas
contaminated with not more than 1 – 3 % hydro-
gen, methane, or nitrogen meets the quality re-
quirements for most downstream chemical pro-
cesses. Hydrogen used for hydrogenation or am-
monia synthesis must meet even more stringent
purity requirements.
Sulfur compounds, acetylene, carbon diox-
ide, and water are removed from synthesis gas
by washing, adsorption, and absorption. This re-
duces the problem to the recovery of pure hy-
drogen or carbon monoxide from a gas mixture
essentially containing hydrogen, carbon monox-
ide, and methane. Cryogenic separation is a
promising route, in addition to selective absorp-
tion and adsorption, for separating the compo-
nents of this gas mixture.
Plant engineering has benefited from several
cryogenic processes, and various process combi-
nations have been used for the respective appli-
cations. Two principal process loops seem to be
promising for carbon monoxide recovery from
synthesis gas mixtures: (1) partial condensation
and (2) the liquid methane wash process. A third
process — the liquid nitrogen wash process — is
used to recover hydrogen for ammonia synthe-
sis.
5.6.1. Partial Condensation
The first stage of the partial condensation pro-
cess for recovering hydrogen or carbon monox-
ide from synthesis gas mixtures is the lique-
faction of higher boiling gas components such
Gas Production 123
as carbon monoxide and methane. Depending
on the pressure applied, liquefaction begins at
ca. −100 to −180 ◦ C, and ends when the sub-
limation temperatures of methane and carbon
monoxide are reached.
The first components to liquefy in a hydro-
gen atmosphere are methane and carbon monox-
ide. Separation of the gaseous and liquid phases
alone yields relatively pure product flows.
Because carbon monoxide recovery requires
temperatures as low as −200 ◦ C, for a cryogenic
process to work properly all components that
may freeze and clog the piping must be removed
completely.
In partial condensation, carbon monoxide is
condensed along “cold walls.” This leaves a
quantity of carbon monoxide, corresponding to
the carbon monoxide vapor pressure, uncon-
densed. The “cold wall” is produced in a heat
exchanger by flashing liquid carbon monoxide
to the lowest possible pressure and evaporating it
in countercurrent. This defines the coldest point
of the partial condensation process: it is the tem-
perature of liquid carbon monoxide evaporating
at the lowest possible pressure [215, 216].
If the carbon monoxide condensate contains
an unacceptably high percentage of methane,
this must be removed by distillation. The car-
bon monoxide yield is 75 – 80 %. Losses are due
to uncondensables in the hydrogen flow and to
carbon monoxide removed along with methane.
However, recovery of only part of the carbon
monoxide may be desirable if hydrogen gas con-
taining a certain proportion of carbon monoxide
is required.
Process Description. Figure 69 shows a typ-
ical process flow diagram of a partial conden-
sation unit. After all contaminants that might
freeze and clog the piping have been removed
from in a pretreatment stage, the gas mixture
is cooled in heat exchangers (a) in countercur-
rent to the cold products coming from the plant.
Part of the carbon monoxide and methane is con-
densed, and the gas and liquid are separated in
a separator (b). Hydrogen gas, which still con-
tains some carbon monoxide, is reheated. The
liquid containing traces of dissolved hydrogen
and methane is depressurized; dissolved hydro-
gen boils off and is removed in the downstream
separator (c). The liquid, which no longer con-
tains any hydrogen, is fed to a column (d) where
the carbon monoxide – methane mixture is sep-
124 Gas Production
Table 30. Typical analyses for the process flow diagram shown in
arated into pure carbon monoxide and a methane Figure 69
fraction containing a certain percentage of car- Feed gas H2 CO Residual
bon monoxide. All cold products are evaporated fraction product gas
at ambient pressure and heated in countercur- Without expander
stage
rent to the hot incoming gas mixture. The car-
Analysis, mol%
bon monoxide yield may be increased by modi- H2 70 88 1.5 40
fying the process by additional process steps and CO 27 12 98.5 50
recycling of carbon monoxide containing flash CH4 3 10
Volume parts 1000 650 50 300
gases. With expander stage
Analysis, mol%
H2 70 96.5 1.5 40
CO 27 3.5 98.5 50
CH4 3 10
Volume parts 1000 600 100 300

5.6.2. Liquid Methane Wash Process

Liquid methane is used to wash a pressurized

Figure 69. Cryogenic partial condensation process
a) Heat exchanger; b) Separator; c) Degasser; d) CO – CH4
separator; e) Expander
In this process, hydrogen is obtained at its
full pressure, which is not always required in
a carbon monoxide recovery unit. The hydro-
gen produced can, therefore, also be used for
flash refrigeration in an expander (e). This pro-
cess element enables the coldest temperature to
be lowered by ca. 20 to −200 ◦ C, so that the
amount of carbon monoxide remaining in the
gaseous phase is greatly decreased and the car-
bon monoxide yield increased [215, 216]. Pro-
cess results are given in Table 30.
hydrogen flow slightly above the freezing point
of methane (i.e., ca. −180 ◦ C). During this pro-
cess, carbon monoxide carried along with hy-
drogen is dissolved in methane; 100 % of car-
bon monoxide in the feed is recovered [217] so
that hydrogen leaving the column overhead is
free of carbon monoxide. For calculation meth-
ods applicable to isothermal wash processes, see
[218].
Spent methane is regenerated by distillation,
expelling carbon monoxide overhead. By us-
ing the heat pump principle and employing a
flash refrigerator, carbon monoxide can be con-
veniently recycled and used to maintain the re-
frigeration balance.
Process Description (see Fig. 70). Pre-
treated synthesis gas is cooled in a heat ex-
changer (a) to the washing temperature of
−180 ◦ C. High-boiling components are thus
condensed, and only the gaseous carbon monox-
ide in the hydrogen gas is washed out with meth-
ane in column (b). This washing methane, meth-
ane from the gas mixture, and carbon monox-
ide that has been condensed or washed out are
fed to the carbon monoxide – methane separator
(c). There, the carbon monoxide product is dis-
charged overhead while the washing methane
remains as the bottom product. A liquid meth-
ane pump (d) delivers the washing methane via
a supercooler (e) to the top of the wash column
(b), from which carbon monoxide-free hydrogen
is discharged overhead. The product streams of
carbon monoxide, hydrogen, and residual meth-
 Gas Production 125

Figure 70. Liquid methane wash process

a) Heat exchanger; b) Liquid methane wash column; c) CO – CH4 separator; d) Liquid methane pump; e) Liquid methane
subcooler; f) Recycled CO expander; g) Recycled CO compressor

ane are heated in the exchanger (a), flowing in contains the following undesirable substances
countercurrent to the feed gas, and recovered in- and contaminants:
dividually.
1) traces of unreacted oxygen from the gasifica-
The carbon monoxide compressor (g) closes
tion process,
the refrigeration loop with the expander (f). The
2) residual methane from unreacted hydrocar-
same compressor may also be used to adjust the
bons,
carbon monoxide product to the required bat-
3) some unconverted carbon monoxide, and
tery limit pressure. Process results are given in
4) argon that entered the system together with
Table 31.
the oxygen required for gasification
Table 31. Typical analyses for the process flow diagram shown in
Figure 70 Whereas argon and methane in the synthesis
Feed gas H2 CO Residual gas are inerts and would unnecessarily burden
fraction product gas the ammonia synthesis loop, the residual oxy-
Analysis, mol% gen and carbon monoxide are poisonous to the
H2 70 98.5 1.7
CO 27 98.5 ammonia synthesis catalyst. Except for an un-
CH4 2 1.5 0.1 100 avoidable residue of argon, the above-mentioned
Volume parts 1 000 705 275 20 contaminants are all eliminated by means of a
liquid nitrogen wash unit.
The refrigeration needed for this process is
obtained by flashing the required amount of ni-
5.6.3. Liquid Nitrogen Wash Process trogen for washing the synthesis gas into the pu-
rified hydrogen already in the cryogenic unit. By
A finishing treatment in a liquid nitrogen wash mixing the nitrogen with the hydrogen stream,
unit is the last process stage in the recovery of the pressure of the cryogenic nitrogen is lowered
hydrogen for ammonia synthesis from hydro- from the full process pressure at which the pure
carbons. In preceding stages, carbon monoxide nitrogen is cooled to the nitrogen partial pres-
is converted to carbon dioxide, producing addi- sure in the hydrogen stream, which more or less
tional hydrogen, and carbon dioxide is then elim- reflects the proportion of nitrogen (24 – 25 %) in
inated completely from the synthesis gas. Hy- the synthesis gas. Essentially, the positive excess
drogen gas entering the liquid nitrogen wash unit enthalpy ∆H occurring during this process pro-
126 Gas Production

vides the refrigeration necessary for the entire
process [219].
Wash nitrogen containing the dissolved con-
taminants is discharged from the column bottom,
flashed to a lower pressure, evaporated, heated,
and discharged as residual gas (for process re-
sults, see Table 32).

Table 32. Typical analyses for the process flow diagram shown in
Figure 71
H2 gas N2 gas Synthesis Residual
gas gas
H2 94.11 mol % 75 mol % 8.31 mol %
N2 0.05 mol % 100 mol % 25 mol % 26 mol %
O2 ppm ppm 2 ppm ppm
Ar 0.60 mol % 50 ppm 7.14 mol %
CO 4.44 mol % 5 ppm 52.68 mol %
CH4 0.50 mol % 10 ppm 5.87 mol %
Volume
parts 1000 337 1253 84

5.7. Gas Separation by Membranes (→

Membranes and Membrane Separation
Processes)

Fundamentals. Certain materials, when

Figure 71. Liquid nitrogen wash unit
a) Heat exchanger; b) Wash column; c) Valve for wash ni-
trogen; d) Refrigeration valve; e) Trim valve
Process Description (see Fig. 71). Hydro-
gen gas containing contaminants such as oxy-
gen, argon, carbon monoxide, and methane is
cooled to ca. −180 ◦ C in a heat exchanger (a).
At a temperature around its dew point, the gas is
fed to the bottom of the wash column (b). Liquid
nitrogen trickling down countercurrently to the
hydrogen gas dissolves the contaminants and is
discharged with them from the bottom of the col-
umn. The overhead product is purified hydrogen
with an nitrogen content that reflects the equi-
librium stage of a hydrogen – nitrogen mixture
at the of temperature and pressure prevailing at
the top of the column. Nitrogen required in the
wash unit is compressed to the process pressure,
cooled in an exchanger (a), and fed to the wash
column through a valve (c). Nitrogen needed for
refrigeration is cooled in the same way, flashed
through a valve (d) into the purified hydrogen,
and evaporated in the exchanger (a) in counter-
current to the uncooled and untreated hydrogen
and the nitrogen flow. The valve (e) is used to
add nitrogen to establish the hydrogen – nitro-
gen ratio (3: 1) required for synthesis.
produced in the form of nonporous membranes
of defined thickness, absorb gas components
in their molecular structure at different rates
and allow them to diffuse through the mem-
brane with a certain pressure drop. The diffu-
sion rate depends on (1) the type of material,
(2) the size of the molecules, (3) the pressure
differential across the membrane, and (4) the
diffusion length (membrane thickness) and ac-
tive area of the membrane. The following types
of membrane can be distinguished:
Polymer membranes
Carbon membranes with micropores
Liquid membranes
Metallic membranes
Ceramic membranes
Whereas membranes based on ceramics, metals,
and liquids have been known for a long time and
have been developed to an industrial standard for
some applications (e.g., palladium ceramics for
the production of highly pure H2 ), the develop-
ment of polymer membranes for gas separation
[220 – 225] has been accelerated since 1977 by
the rapid development of reverse osmosis mem-
branes for seawater desalination [226].
Several gas separation membrane systems,
which compete in materials and design of the
modules, can be found on the market:

1) Prism separator (Monsanto), an asymmetric
porous membrane on a polysulfone carrier
with a nonporous silicon-based coating, in the
form of hollow-fiber bundles;
2) Delsep (Delta Engineering Corporation), an
asymmetric porous membrane based on cel-
lulose acetate with a nonporous cellulose
acetate-based coating, in the form of a coil-
type module with a flat membrane;
3) Separex (Air Products Company); and
4) RO membranes (DuPont), asymmetric porous
membranes based on aromatic polyamide or
cellulose acetate with a nonporous aramid-
based coating, in the form of hollow-fiber bun-
dles.
Applications. Hydrogen and helium have
the best sorption and diffusion behavior of all
gas components, and their separation efficiency
is very good in comparison to nitrogen, meth-
ane, carbon dioxide, or carbon monoxide. Such
gas separation units are, therefore, employed to
recover hydrogen from reaction gas mixtures by
using the same process principle as shown in
Figure 72 in all cases.
Process Description. Case 1: Gas Separa-
tion Membrane installed in a Slipstream. Purge
gas which must be extracted continuously from
a synthesis gas loop (as installed for the ammo-
nia production) to keep down the level of un-
desirable ballasts and nonreacting components
essentially contains the same valuables as the
loop (e.g., H2 , N2 , or CO). To improve overall
efficiency of the synthesis loop, these valuables
can be recovered by means of a gas separation
membrane and recycled at low pressure to the
suction side of the raw gas compressor. Those
gas components that do not permeate the mem-
brane (e.g., CH4 , Ar, CO, higher hydrocarbons)
remain in the waste gas. Typical gas composition
is shown in Table 33.
Table 33. Typical gas composition for purge gas treatment
Raw gas Permeate
H2 , vol % 74 96
CO, vol % 26 4 43
Flow rate, kmol/h 100 43.6
Yield H2 : 56 %
Case 2: Gas Separation Membrane in the
Main Stream. Hydrogen sulfide and carbon
Gas Production 127
dioxide exhibit much better sorption and dif-
fusion behavior than the product gases carbon
monoxide and methane. This favorable separa-
tion efficiency can be used in a pretreatment
stage to reduce the size of downstream conven-
tional fine treatment (see Fig. 73). Most of the
sour gases are removed by the gas separation
membrane, although some valuable components
are lost as well. Such losses of valuable com-
ponents can be minimized by splitting the pro-
cess into several stages and recycling the gases
— a method which, of course, requires addi-
tional energy. Being preceded by a membrane,
the absorption unit is turned into a fine treatment
stage, whose dimensions and complexity can be
reduced considerably.
5.8. Addition of Inerts or Other
Substances
Normally, the quality of a gas is described not
only by its composition but also by such charac-
teristics as its calorific value and Wobbe index
(see Chap. 8).
These characteristics are adjusted as neces-
sary, either by adding inerts such as nitrogen or
air to decrease the calorific value and increase
the density of a gas, or by adding high-calorific
substances such as liquefied gas, butane, or gaso-
line to increase the calorific value. Proper mix-
ing is achieved by installing flow turbulators,
providing spray injection of liquids into the gas
stream, or adding densifiers.
If air is added, the oxygen level in the gas
must be watched closely. Explosive air – gas
mixtures, which may occur briefly in areas
where air is injected into the gas, can be elimi-
nated by flow turbulators.
If liquefied natural gas is used as feedstock, it
can be conditioned to the required calorific value
by adding liquefied nitrogen in the cryogenic liq-
uid phase. Proper mixing is ensured as the gas
evaporates at discharge pressure. This condition-
Waste gas ing method saves energy because only a mini-
57 mum of energy is required to pump the liquefied
56.4
natural gas and liquefied nitrogen, rather than
CO: 93 % necessitating installation of compressor stations
for natural gas, nitrogen, or the gas mixture.
Substances with a manifest odor—usually
higher mercaptans—are added to normally odor-
less gases to warn of any leaks.
128 Gas Production

Figure 72. Principle of H2 recovery from reaction gas mixtures by means of gas separation membranes
a) Gas separation membrane; b) Raw gas compressor; c) Recycle gas compressor

Figure 73. Pretreatment by means of gas separation membrane

a) Gas separation membrane (pretreated stage); b) Sour gas treatment; c) Absorption (fine treatment)

6. Handling of Byproducts 6.1. Aqueous Condensates

Cooling the crude product gas leads to the forma-
tion of aqueous and hydrocarbon condensates.
Usually, water-insoluble hydrocarbons are re-
moved from the aqueous phase and handled sep-
arately. Treatment of the condensates and the
crude gas also results in gaseous byproducts.
Rates and Components. All production
methods for gases containing carbon monoxide
and hydrogen primarily generate a hot crude gas
mixed with water vapor, regardless of feedstock.
The water content of the crude gas originates

from the feedstock moisture (coal), unconverted
gasification steam, or reaction water (oxidation
of part of the feedstock hydrogen). Cooling the
crude gas produces aqueous condensates laden
to a greater or lesser extent with organic or in-
organic substances, depending on the type of
feedstock and the gasification method. Table 34
shows typical condensate rates and contents of
dissolved or suspended components for some
feedstocks and selected gasification methods.
The numbers may change depending on gasi-
fication conditions. As a rule, condensate rate
and impurity content increase with decreasing
gasification temperature and increasing feed-
stock complexity [227 – 231]. In addition to
the classical feedstocks nowadays a variety of
waste materials are used. These have to be pre-
pared, e.g., by pelletizing using suitable binders
such as bituminous coal and/or by mixing with
coal in certain ratios between 50 % and 85 %.
The waste includes solid and liquid materials
like plastics, sewage sludge, rubber, fluff, con-
taminated wood, residues of paint, household
wastes, industrial waste, etc., as well as tar/oil
from fixed bed gasifiers, used oils, solvents
etc. [232]. This changes the composition of the
condensates slightly. The modern practice is to
select gasification types and conditions in such
a way that the condensates obtained are as clean
as possible and/or show low specific rates, in
order to reduce the wastewater treatment cost
(see Chap. 4).
Typical Specifications of Treated Waste-
water. Condensates are recycled as far as possi-
ble within the gas production plant. Only excess
condensate must be specially treated. Treatment
methods depend on the final destination of con-
densates:
1) Use as boiler feedwater (liquid disposal),
2) Use as cooling water make-up (gaseous dis-
posal),
3) Burning of contents and evaporation of water
(gaseous disposal), or
4) Release to receiving water (liquid disposal).
The first two are possible only if the con-
densates contain easily removable components
(e.g., using steam reforming condensate as
boiler feedwater after degassing) or are cleaned
by various treatment processes (e.g., using coal
pressure gasification condensate as cooling wa-
Gas Production 129
ter after tar – dust separation, filtration, extrac-
tion, stripping, adsorption, biological oxidation,
etc.) [233, 234]. Burning is limited by the
amount of water to be evaporated, the environ-
mental impact of sulfur and nitrogen oxides,
and economic aspects (proportion of recover-
able heat). In practice, incineration of gas con-
densates has been considered only for small rates
[235] or for the concentrated residues after treat-
ment [236].
The last method is the most common: gas
condensates are treated to meet wastewater spec-
ifications (local authority regulations) so that the
effluent can be discharged into receiving water
(river, canal, lake, sea).
No universal wastewater disposal standards
exist. Specifications must be negotiated with
the local water control authority, which usually
considers the plant location, type of feedstock,
conversion process, and type of receiving water
[237, 238]. Typical wastewater specifications for
authorized effluent disposal are listed in the fol-
lowing material [BOD5 = biological oxygen de-
mand (five days)], indicating the targets for var-
ious wastewater treatment processes described
in the following sections.
Temperature max. 30 ◦ C
pH 6.5 – 8.5
Suspended solids max. 30 mg/L
BOD5 max. 30 mg/L
COD max. 500 mg/L
Hydrogen sulfide max. 0.1 mg/L
Ammonia (measured as nitrogen) max. 200 mg/L
Free cyanide max. 0.5 mg/L
CNS− max. 15 mg/L
Monohydric phenols max. 0.1 mg/L
Total phenols max. 10 mg/L
Substances extractable with
petroleum ether max. 20 mg/L
6.1.1. Mechanical Treatment
Gravitational Separation. Suspended
solids such as soot, char, or ash and entrained tar
or oil are removed mechanically from gas con-
densates. In coal pressure gasification plants,
the first cleaning step is usually carried out in
tar separators, often followed by additional oil
separators. In oil gasification plants, soot is usu-
ally extracted with oil or naphtha and recycled
to the process.
130 Gas Production
Table 34. Specific rates and composition of gas condensates
Process examples Lurgi coal pressure gasifier British Gas – Lurgi slagging Texaco, Shell,Lurgi MPG Steam reforming
gasifier
Type moving bed moving bed partial oxidation catalytic
Feedstock bituminous coal bituminous coal heavy vacuum residue naphtha
Specific rate of feed, m3 /t 0.7 – 1.2 0.15 – 0.2 0.4 0.5 – 0.7
COD, mg/L 25 000 2400
BOD5 , mg/L 8000 1000
Composition, mg/L
Suspended solids 100 120
Suspended oil 1000 20
Free ammonia 15 000 20 000 1500
Fixed ammonia 350 3 000 150
CO2 30 000 40 000 2400 400
H2 S 700 600 1600
HCN 50 100 300
Monohydric phenols 4500 4000 <1
Total phenols 6000 5000 <1
Dissolved organic 500
substances
Halides (Cl− , F− ) 250 4000
Fatty acids 800 500 400
Nickel 0 2–5
Iron 4 6 – 15
Vanadium 0 3–8
pH 8–9 8–9 8–9 5–7

Primary tar separators may be simple tanks
provided with a feed nozzle, an expansion gas
exit to release dissolved gases, an oil skimmer,
and drawoffs for tar, solids, and cleaned water.
Oil has a lower density, and tar – dust a higher
density, than water so they form top and bottom
layers that are withdrawn while water is obtained
in the intermediate layer. The settling area of tar
and oil separators is usually designed to remove
all particles having a settling velocity higher than
1 – 3 m/h from the aqueous phase. Remaining
particles are removed in the following filtration
step.
Part of the mixture of tar and dust (heavy tar)
is recycled to the gasifiers by positive displace-
ment pumps. Excess tar sometimes undergoes
further dust removal and is sold as a product.
After primary tar separation, the gas condensate
still contains up to 100 mg/L of solids and 500
– 5000 mg/L of tar and oil [239].
The gas condensate is cleaned further in oil
separators down to a content of oil and solids
in the range of 20 – 50 mg/L. The efficiency
of these separators can be enhanced by fitting
a large number of parallel corrugated plates,
which not only increases the settling area but
also achieves laminar flow conditions, resulting
in low Reynolds numbers. An example of this
separator type is the Shell CPI [240].
Filtration. The following treatment steps
(e.g., extraction, stripping, adsorption) require
that tar and solids content be reduced to 10 mg/L
or lower. This can be done in simple gravel fil-
ters operated at low specific loads of ca. 5 – 7
m3 m−2 h−1 . Modern dual- or multimedia filters
can operate up to 20 m3 m−2 h−1 . In dual-media
filters, the gas condensate flows first through an
upper layer of lower density, coarse filter media,
which allows finer solids to penetrate deeply into
the filter bed, and then through a lower layer of
finer filter media to ensure final cleaning.
Filters operate batchwise. Filter beds loaded
with tar and solids are regenerated by backflush-
ing with (hot) water. Usually, the bed is also
loosened by blowing gas through it. After clean-
ing, filter bed particles are classified according
to Stokes’ law by means of an upward stream
of water at a defined rate. The filters not only
remove solids to < 10 mg/L but, at low temper-
atures and low velocities, remove tar and oil as
well. These partly stick to the filter media and
partly collect in the bottom of the filter, from
which they can be removed prior to backflush-
ing. The backflushing liquid (mud liquor) is nor-
mally recycled to the primary tar separator.

Phenol 45
Cresols 30
Xylenols 6 oven and carbonization plants, in the phenol in-
Polyhydric and other phenols 10
Pyridine bases 1 Phenosolvan process the filtered and cooled phe-
Neutral oil, pitch 5
Water 3
6.1.2. Extraction and Adsorption of Organic
Substances
Filtered gas condensates containing high levels
of dissolved organic substances cannot directly
be treated biologically. First, the phenol content
must be reduced to an acceptable level, usually
< 700 mg/L. At low feed rate or concentration,
this is done by dilution. At high concentration of
steam volatile phenols, the condensate is dephe-
nolized prior to stripping the dissolved gases.
This is carried out either by liquid – liquid ex-
traction using organic solvents — e.g., benzene,
methyl isobutyl ketone (MIBK), butyl acetate,
or diisopropyl ether (DIPE) — or by adsorption
on activated carbon. Combinations of these pro-
cesses are also possible [241 – 243]. Adsorp-
tion on activated carbon is mainly used for post-
treatment after dephenolization and/or biologi-
cal treatment of condensates in gas production
plants [244 – 246].
Phenol Recovery by Solvent Extraction.
Figure 74 shows a typical phenol extraction pro-
Figure 74. Lurgi Phenosolvan process for phenol recovery (with steam-saving solvent recovery by gas recycle)
a) Extractor (mixer – settler); b) Fractionator; c) Solvent absorber; d) Solvent stripper
Gas Production 131
cess used in gasification plants, as well as in coke
dustry, and in coal hydrogenation plants. In the
nolic effluent is treated countercurrently with a
suitable solvent such as DIPE in a multistage ex-
tractor. The extract is separated by fractional dis-
tillation into pure solvent (overhead product) and
crude phenols (bottoms product). The solvent is
recycled to the extractor. The raffinate still con-
tains a small amount of solvent which is reco-
vered by stripping with recycled gas. The solvent
is then removed from the gas by absorption in
cooled and recycled crude phenols, from which
it is subsequently recovered in the stripping sec-
tion of the fractionator. The Phenosolvan process
can be operated with different feedstocks, differ-
ent solvents or solvent mixtures (e.g., benzene
and DIPE or DIPE plus MIBK) [247], and differ-
ent solvent recovery systems (e.g., steam, gas, or
ammonia stripping). All steam volatile phenols
and neutral oils can be recovered almost com-
pletely, but only partial recovery of pyridines,
fatty acids, and dihydric phenols is possible. The
suitability of this process for hard-to-extract or-
ganics is limited only by economics, because
residual phenols and other organics can be re-
moved more cheaply by adsorption or biologi-
cal treatment. The intermediate phenol content
between extraction and final treatment is best
determined by means of an economic optimiza-
tion study, an example of which is shown in Fig-
132 Gas Production
ure 75. An advantage of solvent extraction is
the recovery of crude phenol by fractionating
the extract which contains valuable byproducts.
Typical composition of a Phenosolvan extract
from coal pressure gasification is given below,
in percent by weight:
Figure 75. Economical phenol recovery point between phe-
nol extraction and final treatment (typical, e.g., for coal gasi-
fication condensates containing ca. 4500 mg/L monohydric
and ca. 1500 mg/L polyhydric phenols)
a) Extraction; b) Biological treatment; c) Total cost;
d) Biological and activated carbon treatment
If large gas condensate flows must be
dephenolized, extraction must be performed in
mixer settlers, exhibiting high stage efficiencies.
Lower flow rates can be treated in extraction
columns by using many stages to compensate
for low efficiency.
Recovery by High-Pressure Extraction.
Organics can also be recovered by using super-
critical solvents [248]. This method might be
economical for small condensate rates with high
feed concentrations of phenols and other valu-
able organics, but it is not yet being used in gas
production plants [249]
6.1.3. Removal and Recovery of Ammonia
and Sulfur
Before gas condensates rich in dissolved gases
(NH3 , CO2 , HCN, H2 S) can be treated in bio-
logical oxidation or in heavy-metal precipitation
plants, they must be stripped with gas or steam to
decrease free ammonia to < 50 mg/L, hydrogen
sulfide to < 1 mg/L or hydrogen cyanide to <
10 mg/L, or to lower the pH (previously 8 – 9)
to 6. This is done in the total stripper common
to all removal or recovery processes. Its primary
purpose is to produce stripped gas condensate as
bottom product. The overheads contain all the
free gases and water vapor. Processes differ in
the method of treating this gas mixture.
Total Stripper. Depending on the major feed
contaminant, this stripper has different names
such as ammonia still and sour water, hydro-
gen sulfide, or hydrogen cyanide stripper [250].
It usually operates at normal atmospheric pres-
sure, but the pressure may be adjusted depending
on the destination of the top gases. Typical steam
consumption is 140 – 250 kg of steam per cubic
meter of gas condensate.
The stripper is usually equipped with a top
condenser to reduce the water content of the
gases from > 90 to < 50 %.
Incineration, Catalytic Oxidation and Sul-
fur Recovery. The mixture of ammonia, sour
gases, and water can be flared off only if the envi-
ronmental impact (e.g., of SO2 , NOx ) is accept-
able. Otherwise, a special incineration plant with
flue gas treatment is required. Ammonia can also
be removed by catalytic oxidation [251].
If a Claus plant (→ Sulfur, Chap. 6) is avail-
able, the strip gas can be mixed with the feed
for sulfur recovery and ammonia oxidation. If
the ammonia flow is too high compared to the
Claus sulfur stream, the strip gas must be divided
into an ammonia-free sour gas and an ammo-
nia stream low in hydrogen sulfide [252]. Both
streams are fed separately to the Claus plant; first
the ammonia stream is oxidized above stoichio-
metric conditions and then mixed with the sour
gas stream at below stoichiometric conditions to
produce sulfur. Any NOx formed in the first step
reacts with sulfur produced in the second step;
thus, both sulfur dioxide and NOx emissions are
eliminated [253].

Recovery of Ammonia. If the ammonia
quantity exceeds a certain level, incineration
is unacceptable but recovery becomes economi-
cal compared to (catalytic) oxidation. Formerly,
the strip gases were washed with sulfuric acid
to obtain ammonium sulfate, and the remaining
acid gases were fed to sulfur recovery plants. Be-
cause ammonium sulfate sales today are limited,
the recovery of anhydrous or aqueous ammo-
nia is preferred in most cases. Generally, two
different methods are available for the difficult
separation of basic and acid gases from aqueous
solution:
1) Chemical methods using agents that selec-
tively absorb ammonia under certain condi-
tions, but release ammonia under regeneration
conditions [254]; and
2) Physical methods (without agents), based on
different vapor pressures of ammonia and acid
gases at different concentrations in aqueous
solution and at different temperatures or pres-
sures [242, 255, 256][257].
The first method is represented by the
Phosam-W process (U.S. Steel, USX Engineers
& Consultants, Aristech Phosam-W), and the
second by the CLL ammonia recovery process
(Chemie Linz/Lurgi) or by the WWT process
(Chevron); both types of processes are used
in coal pressure gasification plants [258 – 261].
The largest plant worldwide for the recovery of
clean liquid ammonia from coal pressure gasifi-
cation wastewater operates in Secunda at Sasol
II and III since 1980. Both CLL trains together
have a total capacity of 1000 t NH3 per day
formed as a byproduct.
Phosam-W Process (see Fig. 76). The total
stripper (a) overheads are treated in the ammonia
absorber (b) with lean ammonium phosphate so-
lution, which selectively absorbs ammonia un-
der prescribed conditions. The wet overhead
acid gases are dried (c) and sent to a sulfur recov-
ery unit. The rich ammonium phosphate solution
is regenerated in the Phosam stripper (d) at high
temperature and recycled to the absorber. The
stripper overheads (mainly ammonia and water)
are condensed, treated with sodium hydroxide
to bind coabsorbed acid gases, and fractionated
to yield pure anhydrous ammonia as final prod-
uct. Hot (475 K) fractionator bottom water and
sodium hydroxide are flashed into the total strip-
per.
Gas Production 133
Figure 76. Phosam-W process for chemical separation of
aqueous ammonia – acid gas mixture
a) Total stripper; b) Phosam ammonia absorber; c) Acid gas
drier; d) Phosam ammonia stripper
Clean Liquid Ammonia Recovery Pro-
cess (CLL; see Fig. 77). The total stripper
(a) overheads are treated in the acid gas absorber
(b) and ammonia stripper (c) column. Ammonia
is cleaned by fractional condensation and fed to a
liquefaction unit, to yield anhydrous ammonia as
final product. Alternatively, ammonia can be ab-
sorbed in water or fed into the ammonia pipeline
of the factory (Chemie Linz). The acid gas ab-
sorber bottoms are concentrated in the ammonia
stripper (c) and fed to the deacidifier (d) where
clean carbon dioxide and hydrogen sulfide are
obtained as top product, suitable for use directly
as sulfur recovery feed gas.
Deacidification is enhanced by dilution with
water or elevation of temperature and pressure.
Deacidified gas condensate is fed to the total
stripper, closing the CLL loop.
The gas condensate is fed either to the deacid-
ifier if it contains more acid gases and/or inert
gases and/or traces of solvent from the dephe-
nolization step or to the total stripper if it con-
tains more ammonia. Diluted condensates are
also fed to the total stripper.
Both processes described yield ammonia
qualities comparable to synthetic ammonia (Ta-
ble 35); hence, process selection depends on
economic considerations.
134 Gas Production

such as fatty acids, dihydric phenols, and an-

ions (e.g., chlorides and fluorides). Usually, the
COD and BOD of pretreated gas condensates
are decreased biologically. Aerobic microorgan-
isms break down and metabolize most of the or-
ganics to carbon dioxide and produce sludge.
Essentially, two methods exist for aerobic
treatment of gas condensates. The activated-
sludge process is most common because it is less
sensitive to variations in feed BOD. The trickle
bed process, in which a film of microorganisms
oxidizes the organics, is seldom used for gas
condensates [262 – 264]. Sometimes PAC (pow-
dered activated carbon) is used, mainly in acti-
Figure 77. CLL Ammonia recovery process for physical vated sludge processes [265 – 269].
separation of aqueous ammonia – acid gas mixtures If the biotreated gas condensate is to be (part-
a) Total stripper; b) CLL ammonia stripper; c) CLL acid gas
absorber; d) Deacidifier
ly) reused (e.g., as boiler feedwater), final filtra-
tion for removal of suspended solids and, if nec-
essary, ion exchange (→ Ion Exchangers), re-
Table 35. Typical composition of anhydrous ammonia verse osmosis, or multiple flash evaporation for
Clean liquid Synthetic ammonia removal of strong anions may be employed as
ammonia well.
recovered from
gas condensates
Water (added), wt % 0.01 – 0.2 0.2 Activated Sludge Process. For aftertreat-
Ammonia, wt % 99.99 – 99.8 99.8 ment of gas condensates, a single stage con-
Oil, ppm <2 <5
Organic substances, ppm <8 not determined sisting of an activated sludge basin equipped
H2 S, ppm <1 not determined with aerators, to provide the required oxygen
CO2 , ppm <50 not determined and effect mixing of the basin contents, and a
clarifier for separation and thickening of the
activated sludge is usually adequate. Nutrients
Economic Considerations. Chemical ab- (phosphorus and nitrogen compounds) for the
sorption – regeneration plants usually have low microorganisms are needed in the ratio of BOD:
capital costs but high operating costs because N: P = 100: 5: 1. Gas condensates normally con-
of the use of stronger agents and the need for tain the required nitrogen in the form of fixed
high-pressure steam to regenerate the chemicals. ammonia; phosphorus must usually be added in
Chemical absorption plants are less flexible with the form of phosphoric acid.
respect to overload, since the agents have a dis- Typical design figures for biological after-
tinct limit of loading capacity. Physical absorber treatment of gas condensates to achieve a resid-
– stripper plants have higher capital costs but ual BOD5 of 20 ppm are listed in the fol-
lower operating costs because of the use of lowing material (MLSS = mixed liquor – sus-
cheaper steam. The higher the gas condensate pended solids, water-free; BOD5 = biological
flow rate or the ammonia feed concentration, the oxygen demand (five days); DO = dissolved
more economical are physical methods; chemi- oxygen).
cal methods are more economical in the case of
low flow rates or low ammonia feed concentra- Activated sludge basin:
tions. Specific volumetric load,
kg COD m−3 d−1 ca. 1.00
Specific sludge load,
kg BOD5 kg−1 MLSS d−1 ca. 0.25
6.1.4. Biological and Final Treatment Specific sludge content, kg MLSS/m3 ca. 4.00
Oxygen content, ppm DO 1–2
After extraction and stripping, gas condensates Oxygen demand, kg O2 /kg BOD5 ca. 1.50
still contain organic and inorganic substances Specific oxygen transfer, kg O2 kW−1 h−1 ca. 2.50

Postclarification basin:
Retention time, h ca. 2.50
Rise rate (water), m3 m−2 h−1 ca. 0.80
Specific area load, kg MLSS m−2 h−1 4–5
Addition of PAC to the activated sludge basin
improves removal efficiency in some cases, be-
cause of various favorable properties of PAC:
(1) substances toxic or inhibitory to biodegra-
dation are adsorbed; (2) settling, thickening, and
dewatering characteristics of the sludge are im-
proved; and (3) the sludge age can be increased,
resulting in higher retention times of difficultly
biodegradable organics. Typical PAC consump-
tion is 0.1 – 0.3 kg per cubic meter of gas con-
densate.
6.1.5. Removal of Heavy Metals
Gas Production 135
itation steps, sludge dewatering and filter cake
storage.
Precipitation of vanadium and nickel can be
carried out in one step at pH 9 if all metals are
to be removed in one mixture [273]. This mix-
ture is clarified in a Sedimat (an automatic clar-
ifier) [275], equipped with a central flocculation
chamber to which a coagulant (polyelectrolyte)
is added. The flocculated sludge settles to the
thickening section in the bottom of the Sedimat,
from which it is discharged.
The metal-free effluent is filtered to remove
suspended solids, neutralized with sulfuric acid,
and discharged to receiving water.
Thickened sludge streams from the clarifiers
are filtered in order to reduce the water content
to 70 %.

Wastewater from different processes (refining, 6.1.6. Example of an Industrial Application

coking, metallurgy, fossil fuel conversion, power
generation, and others) contains greater or lesser Gas condensate from a typical Lurgi moving-
amounts of heavy metals. The type and con- bed coal pressure gasification with the following
tent depend mainly on feedstock composition approximate composition, in grams per liter:
[270, 271] and the conditions under which prod-
ucts come in contact with water (process con- Tar (suspended portion only) 11.0
Oil (suspended portion only) 3.5
densates, quench water, cleaning liquid, etc.). Suspended solids 1.5
Some of the wastewater must be treated for Steam volatile phenols 4.6
removal or recovery of heavy metals. Typical Dihydric phenols 0.9
methods are liquid – liquid ion extraction, fixed- Fatty acids as acetic acid 0.7
Soluble organic substances 0.4
bed ion exchange, and precipitation by adding Free ammonia 15.6
suitable chemicals such as metal salts, lye, or Fixed ammonia 0.7
acid [272 – 274]. Carbon dioxide 32.0
Hydrogen sulfide 0.4
In the majority of all cases, gas condensates
Free cyanide 0.1
contain only small quantities of heavy metals. Water balance
However, a considerable nickel and vanadium
content is found, for instance, in gas conden-
sates from partial oxidation of heavy fuel or vac- and a flow rate of 500 m3 /h is to be treated
uum residues. These metals are environmentally so that 20 % can be released to receiving wa-
harmful. The new Lurgi Multi Purpose Gasifica- ter, 75 % used as cooling tower make-up water,
tion (MPG) process provides a special treatment and 5 % used as boiler feedwater. A typical pro-
of the heavy metals (MARS, Metals Ash Recov- cess sequence is shown in Figure 78. Interme-
ery System, see Sections 3.2.2 and 7.2). This diate battery limit conditions should be selected
reduces the metals concentration in the effluents in such a way that total treatment cost is mini-
considerably. mized whereas final conditions are still satisfied
[276]. This leads to the following typical design
Precipitation of Vanadium and Nickel. Af- criteria, in milligrams per liter, for intermediate
ter removal of hydrogen cyanide, carbon diox- product streams (after treatment):
ide, hydrogen sulfide, and ammonia, the stripped
Tar separation
condensate typically has a pH of ca. 6. It is Total suspended matter 1000
cooled to 40 ◦ C and fed to the heavy-metal re- CPI oil separators
moval plant, which consists mainly of precip- Total suspended matter 350
136 Gas Production
Dual media filters (for 500 m3 /h)
Suspended matter 10
Phenosolvan plant
Steam volatile phenols 10
Dihydric phenols 280
Ammonia recovery
Free ammonia 50
Hydrogen sulfide 1
Activated sludge treatment
BOD5 reduction from
700 to
20
Final dual media filtration
Activated sludge content 20
Activated carbon posttreatment (using GAC, Granular
Activated Carbon; [277])
(for 400 m3 /h) Biologically refractory substance 5
Ion exchanger (for 25 m3 /h)
Strong ions 10

In addition, the aqueous condensate treat-

ment units will produce the following valuable
byproducts, in tons per hour:

Tar 5.4
Oil 1.7
Crude phenol 2.7
Sulfur (via Claus plant) 0.1
Clean liquid ammonia 7.9

6.2. Hydrocarbon Condensates

The yield and composition of hydrocarbon con-

densates depend very strongly on the type of
coal and the gasification conditions. In a coun-
tercurrent gasification system (e.g., Lurgi pres-
sure gasification), coal travels through a retort-
ing zone where volatile components are vapor-
ized and leave the gasifier along with the gas.
When the product gas is cooled in subsequent
heat exchangers and coolers, different conden-
sate fractions are recovered. When the temper-
ature drops below the dew point of water, wa-
ter condenses along with the hydrocarbons and
forms an aqueous phase in the final separators
(see Section 6.1).
Two fractions are recovered from Lurgi pres-
sure gasification: a tar fraction containing the
high boilers and an oil fraction boiling in the
medium range. A third light naphtha fraction
is obtained when the gas stream is cooled fur-
ther for low-temperature purification in a Recti-
sol plant.
Figure 78. Treatment of aqueous condensates from moving
bed coal gasifier (example given in the text)
* These processes are optional
Whereas the naphtha fraction can be treated
directly in downstream units, the tar and oil frac-
tions must be pretreated by conventional meth-
ods to remove suspended solid material (ash) and
undissolved water. Typical properties and com-
positions of tar and oil are shown in Table 36.
To obtain products with suitable properties
for use as fuel oil and gasoline, the combined
pretreated medium- and high-boiling conden-
sates are separated into their respective frac-
tions by distillation [278]. Distillate boiling in
the gasoline range is then refined along with the
light naphtha fraction by hydrogenation to re-
move unsaturated compounds (which are poten-
tial gum formers) and to eliminate sulfur and ni-
 Gas Production 137

trogen. Recovery of chemically pure compounds or may be fed to a partial oxidation plant to pro-
such as naphthalene or cresols (isomeric mix- duce synthesis gas.
ture) is usually uneconomic because of the small
amounts present in the condensates [279]. Table 37. Typical fractions from a coal tar distillation unit
Approximate Approximate boiling
Table 36. Typical composition of condensates from Lurgi pressure total, wt % range, ◦ C
gasification Light naphtha 4 ≤170
Heavy naphtha 7 160 – 210
Tar Oil
Medium creosote 25 190 – 290
Rate, wt % of total 60 40
Heavy creosote 21 260 – 400
Total water, wt % 10 – 15 15 – 20
Residual oil 13 max. 5 vol %
Suspended solids, wt % 15 – 25
≤300
Properties after removal of solids
Pitch * 30 max. 15 vol %
and undissolved water
≤350
Specific gravity, d 30 1.05 – 1.1 0.94 – 0.96
Solidification temperature, ◦ C + 15 <− 20 * Softening point of pitch is ca. 70 ◦ C; nonvolatile residue of
Flash point, ◦ C + 60 + 19 pitch, max. 30 wt %.
Water, wt % 4 2
Nitrogen, wt % 1 1 Table 38. Typical feedstocks for hydrorefining (approximate
Sulfur, wt % 0.4 0.4 figures)
C6 – C9 aromatics, wt % 6 16 Heavy Light Light Total
Naphthalene, wt % 3 5 naphtha naphtha naphtha blend
Methylnaphthalene, wt % 3 4 from tar from
Phenolic compounds as cresol, distillation Rectisol
wt % 21 19 unit
Initial boiling point, ◦ C 98 96 Rate, wt % of total 15 25 65 100
Portion distilled at 360 ◦ C, wt % 60 75 Specific gravity, d 20 0.93 0.84 0.83 0.85
Distillation residue, wt % 40 25 Bromine consumption, 114 33 37 70
Properties of distillation residue g/100 mL
Softening point, ◦ C 67 63 Total sulfur, wt % 0.35 0.49 0.42 0.4
Portion insoluble in toluene, Mercaptans, mg/kg 20 70 80 68
wt % 10 7 Phenolic oil, vol % 25 10
Portion insoluble in quinoline, Alkaline nitrogen, mg/kg 10 100 7600 270 5000
wt % 2 0.1 Naphthalene, wt % 10 1.5
Coke (Conradson coking test), Initial boiling point, ◦ C 130 – 140 90 – 95 50 – 55 55
wt % 29 28 Boiling end point at 95 200 – 210 150 – 160 140 – 145 220
wt %, ◦ C
Chemical hydrogen 360 135 60 120
consumption, m3 (STP)/t

6.2.1. Distillation
In a first dewatering column, the water content is
lowered by distillation. The dehydrated hydro-
carbon condensate is then distilled in an atmo-
spheric column. A typical distillation unit yields
six fractions (see Table 37). Light and heavy
naphtha are obtained as top and first side frac-
tions; they are combined with the Rectisol naph-
tha and refined in a hydrogenation unit (see Table
38).
Two more side fractions, heavy and medium
creosote, are recovered from the atmospheric
column. The bottoms fraction is flashed into a
drum under vacuum where it separates into va-
porous residue oil and pitch.
Fractions boiling above 210 ◦ C are used (e.g.,
as fuel or impregnation oil for wood). Pitch is
suitable as a binder for briquetting of fine coal
6.2.2. Hydrorefining
Hydrorefining is used (1) to saturate olefins and
diolefins to their respective alkanes; (2) to con-
vert sulfur in mercaptans and thiophenes to hy-
drogen sulfide; (3) to convert nitrogen in pyri-
dines and amines to ammonia; (4) to convert or-
ganic chlorine to hydrogen chloride; and (5) to
convert oxygen in phenols to water. The feed-
stock is a blend of the various naphtha streams
recovered from condensates (see Table 38).
The Benzoraffin process, developed around
1960 jointly by BASF, Veba-Chemie, and Lurgi
[280, 281], is commercially successful in refin-
ing the pretreated naphtha fractions derived from
coal gasification. It is a fixed-bed, catalytic, gas-
phase hydrogenation process using a cobalt –
molybdenum catalyst operating at ca. 5 MPa and
350 – 420 ◦ C (Fig. 79).
138 Gas Production
Figure 79. Benzoraffin process for hydrorefining of naphtha fractions
a) Feed pump; b) Vaporizer; c) Mixer; d) Prereactor; e) Heat exchanger; f) Reactor; g) Cooler; h) Separator; i) Recycle com-
pressor
Modern alternatives to this process (e.g.,
by BASF, Lurgi-Südchemie, IFP et al.) — also
used for the preparation of feedstocks for
extractive distillation of toluene (→ Toluene,
Chap. 3.1) — also work with two reactors, but
the first reactor contains a palladium catalyst
and operates in the liquid phase at low tempera-
tures, preventing gum formation from diolefins
or styrene.
The feed naphtha contains highly reactive
chemical compounds with a strong tendency to
form resinous deposits in heaters and vaporizers.
A special vaporizer developed by Lurgi avoids
fouling and frequent shutdowns for cleaning.
Process Description. Feed naphtha is vapor-
ized under pressure and mixed with hydrogen-
rich gas in a specially designed vaporizer (b)
[281]. A small stream is withdrawn as residue
from the bottom and returned to the tar distilla-
tion unit. The mixture of gas and naphtha vapor
passes through a prereactor (d) filled with cobalt
– molybdenum catalyst. Here, the most reac-
tive unsaturated compounds are hydrogenated to
prevent fouling in the heat exchanger (e). Reac-
tion occurs at 200 – 250 ◦ C. The outlet temper-
ature is ca. 5 – 10 ◦ C higher due to the exother-
mic reaction. After further heating in the heat ex-
changer (e) to about 350 ◦ C, the prereactor efflu-
ent enters the main reactor (f). This reactor has
two catalyst beds and a facility for injecting re-
cycle gas to adjust the reaction temperature. The
first bed contains cobalt – molybdenum catalyst
pellets; the second bed is filled with a molybde-
num catalyst. The exothermic reaction leads to
an effluent temperature > 400 ◦ C. The gas – va-
por mixture is cooled to 30 – 40 ◦ C in a heat ex-
changer (e) and cooler (g). Water should be in-
jected into the cooler to prevent salt deposits, be-
cause hydrogen chloride and ammonia formed

during the reaction tend to solidify at lower tem-
perature in the form of ammonium chloride.
The condensed raffinate is separated from the
gas in a separator (h). After depressurization to
ca. 1 MPa, the raffinate is stripped in a strip-
per column to remove hydrogen sulfide, ammo-
nia, carbon dioxide, and water. If it still contains
some phenolic compounds, a caustic wash and
a subsequent water wash are recommended. A
portion of the separated gas is withdrawn to re-
move sufficient light byproducts and inerts for
the partial pressure of hydrogen to be adjusted
properly. The main stream is compressed and
recycled to the vaporizer after addition of fresh
hydrogen.
A typical specification for a hydroraffinate
from the naphtha blend in Table 38 is shown
below.
Appearance clear and free of suspended solids
Color, Saybolt 0 tion. Therefore, low investment cost are often
Water max. 0.1 wt %
Total sulfur max. 0.1 wt %
Existent gum max. 4 mg per 100 mL
Aromatics ca. 75 wt %
Because of its high aromatic content, this raf-
finate is a valuable blending component for gaso-
line. Alternatively, pure benzene, toluene, and
other aromatics may be recovered from the raf-
finate by appropriate separation processes. Sol-
vents with specified boiling ranges for various
applications in the chemical industry can be ob-
tained by fractionation.
6.3. Gaseous Byproducts
Sulfur Compounds (→ Hydrogen Sulfide,
see → Sulfur). Hydrogen sulfide constitutes the
main part of the gaseous sulfur components. It
usually accounts for 90 – 95 % of the sum of
all sulfur compounds. The remainder is primar-
ily COS; CS2 , SO2 and mercaptans are usually
present in trace amounts only.
These sulfur components occur in various
waste gases and are more or less strongly diluted
with CO2 . Hence, processing depends totally on
their concentration and usually aims at recover-
ing elemental sulfur. In special cases, the direct
production of sulfuric acid can also be of inter-
est and even low concentrated H2 S gases can be
used for this purpose.
Gas Production 139
There are various methods available for the
recovery of elemental sulfur from low concen-
trated waste gases (e.g., 1 % H2 S, 98 % CO2 and
1 % inert gases). These methods include concen-
tration by selective absorption or by adsorption,
and sometimes intermediate steps with (partial)
combustion to SO2 are also involved. Processes
of this type have been occasionally employed.
From a theoretical standpoint, the most eco-
nomical method should be direct oxidation, ei-
ther in the gaseous or in the liquid phase as per-
formed in an oxidation wash, e.g., the Lo-Cat
process (see Section 5.4.3). However, it should
be taken into consideration that organic sulfur
compounds in the gas, primarily COS and CS2 ,
remain practically unchanged and this could
represent an undue environmental burden. On
the other hand, precautionary measures must be
taken if the waste gas contains trace components,
such as HCN, that could cause solvent degrada-
counterbalanced by high operating cost for sol-
vent reclaiming and/or make-up of chemicals.
Today oxidation wash systems are mainly used
for low-pressure off-gases with low sulfur con-
tents, with limitations in capacity.
If hydrogen sulfide is present in concentrated
form, i.e., in concentrations of more than 20 %
(in some cases 10 % are sufficient) sulfur can be
recovered more economically by using the Claus
process. However, the Claus tail gas almost al-
ways requires an additional treating step; it usu-
ally still contains 3 to 6 % of the sulfur, mainly
in the form of H2 S and SO2 . A modern solu-
tion is the integration of a three stage Doxosul-
freen process (→ Sulfur, Chap. 7.2.1.1) shown
schematically in Figure 80. Here, the first two
catalytic reactors after the combustion chamber
are continuously operated according to the clas-
sical Claus principle. After condensing the ele-
mental sulfur formed in the Claus reactors, COS
and CS2 are converted by catalytic hydrolysis
at elevated temperature. The following reactors
— each containing a Sulfreen stage and a direct
oxidation stage — are operated in cycles: in one,
the Claus reaction is first, at a slight surplus of
H2 S, continued below the sulfur dew point with
adsorption of the newly formed sulfur, and then,
at further reduced temperature, the residual H2 S
is almost completely converted by catalytic ox-
idation with air. In the second reactor, operated
140 Gas Production
Figure 80. Two-stage Claus plant with internal hot gas bypass, integrated Doxosulfreen plant and thermal incineration
a) Claus reactors; b) Sulfur condensers; c) Separators; d) Heater; e) Hydrolysis reactor; f) Cooler; g) Sulfreen and h) Direct
oxidation stages; i) Thermal incineration
in parallel, the sulfur is desorbed by acid recy-
cle gas and is subsequently, as in the first two
steps, separated in liquid form in coolers, with
the generation of LP steam [282].
Carbon Dioxide. Today, there are basically
four different ways of releasing sulfur-free car-
bon dioxide:
– Release into the atmosphere (there might be
restrictions in the future),
– Use for enhanced oil recovery (EOR) or
– As chemical raw material, and
– Recovery as pure CO2 for the food and phar-
maceutical industry.
Usually a large part of the CO2 waste gas is
released into the atmosphere for lack of other
uses, although it should be taken into consider-
ation that even sulfur-free CO2 , in larger con-
centrations, is dangerous (in Germany the MAK
value is 5000 ppm). However, in the case of fur-
naces, a sufficiently high flue-gas temperature
normally ensures adequate dilution in the atmo-
sphere; special precautions are required for cold
process waste gases and the high carbon diox-
ide density relative to air. If introduction into
a flue gas is not possible (dew point!), cooling
towers can be used provided that the danger of
corrosion is taken into account, otherwise, only
special stacks may be employed.
In connection with the general discussion
about the various factors influencing the earth’s
climate and the necessity to decrease the CO2
emission into the atmosphere, several solutions
have been considered theoretically, e.g., the de-
positing of CO2 in absorbed form in deep layers
of the oceans. However, none of these sugges-
tions have been realized so far on a technical
scale.
One of the more modern applications of CO2
is in enhanced oil recovery. The specification for
the CO2 to be injected in aging oil wells (to re-
duce the oil’s viscosity) is usually less stringent:
CO2 concentration 98 %, C1 /C3+ hydrocarbons
up to 0.3 %, total sulfur in the 1 % range. This
purity may often be accomplished simply by de-
hydration of the raw CO2 [283].
Various requirements have to be met for the
use of carbon dioxide as a chemical raw mate-
rial: in the production of carbon monoxide or
synthesis gas from natural gas, which has the
lowest C/H ratio of all raw materials, carbon
dioxide is frequently removed from the process
gas by absorption and recycled to the reformer.
Care must be taken that the catalyst used is not

damaged by solvent vapors or other trace com-
ponents. Waste gases from hot potash, amine,
and physical washes operated with sulfur-free
solvents generally cause no problems, as long
as effective separators are employed which are
usually followed by a re-compression step. This
compression step also contributes to residual
separation.
Carbon dioxide used in the synthesis of urea
has to meet more stringent requirements. Indeed,
a maximum concentration of inert gases, usu-
ally 1 – 2 % of hydrogen and carbon monox-
ide, should not be exceeded and sometimes even
traces of solvents can cause problems. However,
these small amounts can generally be separated
by a simple adsorption step with an appropriate
molecular sieve.
The highest demands are made on the purity
of carbon dioxide used in the pharmaceutical or
food industry, e.g., in the form of dry ice for cool-
ing or packaging purposes or in compressed or
liquid form for the production of beverages. De-
pending on the impurities to be separated (even
a few ppm of odorous substances are often suf-
ficient to cause an unpleasant smell), usually
several different, usually adsorptive, purification
steps are necessary. More modern installations
include also distillation stages (to separate “sour
CO2 ” together with heavier hydrocarbons and
light inerts) as well as oxidation stages to con-
vert the reminder of undesirable hydrocarbons
(Fig. 81) [283, 284].
7. Typical Examples of Complex Gas
Production Plants
7.1. Methanol Production from Natural
Gas
The production of methanol (→ Methanol)
with natural gas (→ Natural Gas) as feedstock
is described by the following process steps:
(1) gas production, (2) methanol synthesis, and
(3) distillation. Details of the three single pro-
cess steps are described in other chapters; this
chapter deals with specific features of the over-
all arrangement.
Basically two different gas production tech-
nologies, steam reforming and catalytic au-
tothermal reforming, or a combination of both
Gas Production 141
are used to produce methanol from natural gas,
depending on plant size and availability of car-
bon dioxide from outside battery limits.
Synthesis gas produced by steam reforming
is characterized by a relatively low pressure and
a surplus of hydrogen. By addition of carbon
dioxide the composition of the synthesis gas can
be adjusted to be more favorable for methanol
production.
Pure catalytic autothermal reforming results
in a synthesis gas with a relatively high pressure
but with a deficiency in hydrogen for methanol
synthesis. A carbon dioxide removal unit is re-
quired or additional hydrogen has to be provided
to adjust the appropriate gas composition. Such
hydrogen may be obtained either from the meth-
anol synthesis purge gas and from additionally
produced reformed gas or from a conditioned
methanol synthesis purge gas.
The combination of both technologies, the so-
called combined reforming process, has the ad-
vantage of an optimum composition and a high
pressure of the produced synthesis gas.
For the methanol synthesis itself a wide
range of technologies are available, which differ
mainly in the design of the methanol converter.
In principle, three different types of converters
are used in the industry; the quench-cooled, the
gas-cooled, and the water-cooled reactor. For op-
timization of the reaction and for capacity in-
crease also combinations of these technologies
are applied.
In the distillation section the raw methanol
produced in the synthesis section is purified to
meet the required specification. Depending on
plant capacity and optimization with regard to
cost or energy savings, a two or three column
concept can be used.
At locations where no carbon dioxide is avail-
able most of the methanol plants are based on
the following gas production technologies, de-
pending on their capacities: steam reforming for
capacities up to 2000 t/d, combined reforming
from 1800 to 2500 t/d [285, 286].
Erection of plants with a capacity of 5000 or
even 10 000 t/d is also discussed nowadays, e.g.,
for minimizing flaring of associated gas in oil
fields by producing methanol as a “liquid stor-
age”. For this size of plants pure catalytic au-
tothermal reforming in combination with a high
efficient conversion of synthesis gas to metha-
nol is the most economical way. The process is
142 Gas Production
Figure 81. Purification of CO2 for the production of beverages
a) Fractionation; b) Adsorptive sulfur guard; c) Catalytic oxidation; d) Adsorptive dryers
designed in such a way that conditioned purge
gas with the required hydrogen content is ob-
tained to adjust the reformed gas composition.
This technology is illustrated in the simplified
process flow diagram in Figures 82 and 83 and
described in Section 7.1.1.
Steam reforming technology and combined
reforming technology are discussed in Section
7.1.2.
7.1.1. Methanol Production Based on
Catalytic Autothermal Reforming (Figs. 82
and 83)
Gas production, methanol synthesis, and subse-
quent distillation are the primary process steps.
The relevant units are combined with an inte-
grated steam system usually on several pressure
levels. Steam is generated and conditioned in
the synthesis, in the reformed gas and flue gas
waste-heat system, and in the auxiliary boiler.
Natural gas is preheated and desulfurized. Af-
ter desulfurization the gas is saturated with a
mixture of preheated process water from the dis-
tillation section, process condensate, and make-
up water in the saturator (d). The gas is further
preheated and mixed with process steam as re-
quired for the prereforming process. In the pre-
reformer (f) the gas is converted to hydrogen,
carbon dioxide, and methane. Final preheating
of the gas is achieved in the fired heater (b). In
the autothermal reactor (g) the gas is reformed
with steam and oxygen, the product gas con-
tains hydrogen, carbon monoxide, carbon diox-
ide, and a very small amount of non-converted
methane and inerts together with undecomposed
steam. The reformed gas leaving the autother-
mal reactor possesses a considerable amount of
heat, which is recovered in form of high pres-
sure steam, preheating energy, and energy for
providing heat for the reboilers in the distilla-
tion section.
The reformed gas is mixed with hydrogen
from the pressure swing adsorption unit to adjust
the synthesis gas composition. Synthesis gas is
pressurized to 5 – 10 MPa by the synthesis gas
compressor (o). Subsequently, this compressed
gas is mixed with recycle gas from the synthesis
loop. With the recycle gas compressor (t), the
recycle: make-up gas ratio can be adjusted. The
inlet gas to the reactor system consists mainly of
hydrogen, carbon monoxide, and carbon dioxide
as reactive components, along with methane and
nitrogen as inerts. This gas mixture is converted
to methanol according to the following exother-
mic reactions:
CO+2 H2
CH3 OH
CO2 +3 H2
CH3 OH+H2 O
Details of the reaction mechanism are de-
scribed elsewhere (→ Methanol). The synthesis
reactor system (q) is the key section of the loop.
Here superheating of the catalyst is avoided by
generation of medium pressure steam and the
reaction parameters are selected in such a way
that properly conditioned purge gas is obtained.
In the pressure swing adsorption unit hydro-
gen is separated from the purge gas and routed
to the reformed gas. The remaining gas is used
as fuel in the fired heater.
The distillation unit is a three-column energy-
saving system. In the light-ends column (u),
low-boiling impurities are removed overhead.

Pure methanol distillation is divided into two
sections. The first section (v) operates at ele-
vated pressure, and ca. 50 % of the methanol
is distilled overhead. In the second section (w),
which operates at ambient pressure, the remain-
ing methanol is separated from water and high-
boiling impurities.
Whereas the first section is heated with low-
pressure steam, heat for the second section is
provided by condensing methanol vapor from
the first section.
7.1.2. Comparison of Conventional Steam
Reforming and Combined Reforming
Processes for Methanol Production
The main reason for applying the combined re-
forming process in methanol production is ad-
justment of the stoichiometric number (SN) as
defined in Table 39, closer to the theoretical
value of 2.0. Whereas the practical SN is bet-
ween 2.6 and 2.9 for conventional steam reform-
ing, it is decreased to 2.03 in the combined re-
forming process.
Table 39. Conventional steam reforming versus combined process
for methanol production
Conventional Combined
steam
reforming
Process natural gas feed to tubular 100
reformer, %
Process natural gas feed to
autothermal reactor, %
Outlet pressure tubular reformer, 1.9
MPa
Outlet pressure autothermal
reactor, MPa
Outlet temperature tubular 875
reformer, ◦ C
Outlet temperature autothermal
reactor, ◦ C
Hydrocarbons converted in tubular 83
reformer, %
Stoichiometric number,


SN = 2.6
 – 2.9
CH2 −CCO2 / CCO +CCO2
Total natural gas lower heating 31.6
value demand, GJ *
Thereof fuel consumption of 12.9
reformer, GJ *
Discharge – suction pressure ratio 4.4
(synthesis make-up gas
compressor)
Instrument air ** separate unit byproduct
Plant air ** separate unit byproduct
Nitrogen ** separate unit byproduct
* Per t of methanol.
** With oxygen generation in an air separation plant.
Gas Production 143
Besides reducing the SN, placement of an au-
tothermal reactor downstream of the tubular re-
former means that the tubular reformer can be
drastically reduced in size for two reasons: first,
it has to treat only about half of the natural gas
feed while the other half is by-passed directly to
the autothermal reactor and, second, it does not
have to convert all of the methane but leaves an
essential part for the secondary reforming step.
So the fired steam reformer may be ca. 75 %
smaller, can operate at lower temperature, and
therefore, can operate at higher pressure than
a steam reformer in the conventional steam re-
forming process.
Because of the lower SN, less surplus hydro-
gen must be compressed and introduced into the
synthesis loop, which results in a significant re-
duction of equipment size and compression en-
ergy. Table 39 shows the main operating data of
the combined reforming process in comparison
with the conventional steam reforming process.
7.2. Hydrogen Production Based on
Heavy Residues
Economic and environmental considerations
have led petroleum refiners to intensify efforts
process
to maximize production of high-quality products
40 – 60 from crude oil. To meet this goal, a number of re-
finery processes have been developed to upgrade
60 – 40 heavy residues to, for instance, naphtha and gas
3.7 oil. Some of these conversion processes (e.g.,
hydrotreating or hydrocracking) require consid-
3.5
erable quantities of hydrogen. Today most of the
780 hydrogen is produced by steam reforming of nat-
ural gas (83 % of total production) or naphtha
950
(14 %). Only 3 % is obtained by gasification of
22 heavy residues [287]. However, though the cap-
ital investment for such a plant is considerably
2.03
higher than for a unit based on steam reforming
29.5 of natural or refinery gas, gasification of residues
can still be advantageous, particularly where nat-
3.1
ural gas or other light hydrocarbons are not read-
2.2 ily available or expensive.
In some refining schemes, particularly those
for treating heavy crudes, the hydrogen bal-
ance of the refinery may require utilization of
the residues for hydrogen production. In addi-
tion, partial oxidation of heavy residues can con-
tribute to reducing the size of the fuel oil pool
144 Gas Production

Figure 82. Methanol from natural gas, catalytic autothermal reforming route — production of synthesis gas
a) Natural gas interchanger; b) Fired heater; c) Desulfurizer; d) Saturator; e) Natural gas preheater; f) Prereformer;
g) Autothermal reactor; h) Waste-heat boiler; i) Circulation water heater; j) Distillation reboilers; k) Final cooler; l) Final
separator; m) Oxygen preheater

Figure 83. Methanol from natural gas, catalytic autothermal reforming route — methanol synthesis
n) Synthesis make-up gas compressor turbine; o) Synthesis make-up gas compressor; p) Heat exchanger; q) Synthesis reactor
system; r) Cooler; s) Crude methanol separator; t) Recycle gas compressor; u) Light ends column; v) Pure methanol pressure
column; w) Pure methanol atmospheric column

and increasing its quality by consuming some of A typical hydrogen specification for a hydro-
the highest sulfur- and metal-containing compo- cracker is
nents of the pool [288].

Hydrogen ≥98 %
Carbon monoxide and carbon dioxide ≤10 – 50 ppm
Oxygen ≤100 ppm
Inerts (N2 , Ar, CH4 ) balance
The raw gas supplied by a partial oxidation
unit fed with a heavy residue contains nearly
50 % carbon monoxide, as well as other com-
ponents (CO2 , H2 S, COS) which must be con-
verted or removed in a number of gas treat-
ment stages to yield acceptable product qual-
ity (see Table 24, example 3). In practice, gas
plants based on partial oxidation are often mul-
tiproduct plants, which in the refinery environ-
ment could imply cogeneration of clean fuel gas
or, for example, methanol for methyl-tert-butyl
ether (MTBE) (→ Methyl Tert-Butyl Ether) pro-
duction.
Selection of gas treating processes must be
made carefully, because ca. 20 – 30 % of the to-
tal investment for an overall hydrogen plant is
concentrated in these units. Plant size and possi-
ble cogeneration of other products also influence
the final choice of process.
For the partial oxidation unit, either of the
three commercially proven processes (Shell,
Texaco, Lurgi) is suitable.
Conventional Gasification-Based Hydro-
gen Production. The principal process steps for
hydrogen production based on heavy residues as
feedstock are as follows (see Figure 55):
– Gasification
– Acid gas removal (H2 S, CO2 ), in one or two
separate units
– CO shift conversion
– Final purification
The byproducts have to be handled within the
refinery (steam, fuel gas) with the appropriate
specifications or should be salable (sulfur, metal
ash).
As outlined in Section 3.2.2, the gasifica-
tion process itself can be applied in two differ-
ent configurations followed by different down-
stream treatment modes of the raw synthesis gas:
1) Gasification in boiler configuration with
downstream CO shift of desulfurized syngas.
2) Gasification in quench configuration with raw
gas shift (see Section 5.1) prior to desulfur-
ization (and CO2 removal).
In the boiler configuration, the sensible heat of
the hot raw gas leaving the gasification reactor
Gas Production 145
is utilized to generate high-pressure steam in a
waste-heat boiler before the gas enters the scrub-
ber. After the subsequent desulfurization and a
clean gas CO shift conversion, CO2 must be re-
moved from the syngas by a second washing
step. This route has been chosen for the Shell
Pernis plant [289]. The disadvantages of this
concept are high capital costs due to the ex-
pensive gasification stage (waste-heat boiler),
CO shift conversion (with cooler-saturator cir-
cuit) and the two-stage acid gas removal unit
along with limited feedstock flexibility due to
the boiler specification. An asset is a rather high
thermal efficiency.
In the quench configuration, the raw gas leav-
ing the gasifier is shock-cooled by direct injec-
tion and subsequent scrubbing with water. It can
thus be routed directly to the sulfided CO shift
conversion (raw gas shift). The steam content of
the quenched gas is normally sufficient for the
shift reaction, which leads to a quite simple lay-
out of the shift conversion plant. Furthermore,
trace components like COS and HCN are de-
stroyed in the shift reactor, which facilitates the
subsequent acid gas removal. This concept has
been proposed by Texaco [290] and Lurgi [291,
292]. The advantage of this concept is lower cap-
ital cost for both the gasification unit and the
shift. A disadvantage is the loss in thermal effi-
ciency.
Improved Route for Hydrogen Produc-
tion. In order to further increase the economics
of a gasification-based hydrogen production unit
compared to a further steam reforming step, the
above described quench configuration route has
been improved by Lurgi introducing the Multi
Purpose Gasification together with an advanced
ash handling system and an optimized CO shift
conversion. The new concept consists of the fol-
lowing process units (Fig. 84):
– Air separation and oxygen compression,
– Multi Purpose Gasification (MPG) in quench
configuration,
– Metals Ash Recovery System (MARS),
– Sulfided CO-Shift (single-stage raw gas
shift),
– Sulfur removal (Rectisol process),
– Pressure swing adsorption (for remaining
CO2 and low concentrated impurities),
146 Gas Production
Figure 84. Block flow diagram of the MPG based hydrogen production
ASU = Air separation unit; MPG = Multi Purpose Gasification; MARS = Metals Ash Recovery System; PSA = Pressure swing
adsorption; SDA = Solvent deasphalting; BFW = Boiler feed water; CW = Cooling water
– Sulfur recovery unit (Claus process).
Two main features make this concept most
economic compared to conventional process
routes:
1) The MPG process with its high feedstock flex-
ibility allows the simultaneous processing of
even the heaviest refinery residues and wastes,
which can reduce the costs for feedstock sup-
ply (see below).
2) In the sulfided CO shift, the raw gas is con-
verted in a single-stage reactor which results
in an increased CO content in the converted
gas. On the one hand, this leads to a lower H2
yield and therefore requires more feedstock to
be processed in gasification. The advantages,
however, are:
– A self-burning PSA off-gas which can di-
rectly be used as fuel gas in an auxiliary
boiler or sent to the refinery’s fuel gas sys-
tem. There is no need for fuel import.
– The capital costs for the overall plant are
reduced because of the cheaper CO shift
conversion and the cheaper CO2 removal.
A simplified process flow diagram of the gasi-
fication and shift conversion section is shown in
Figure 85. The raw gas is produced by partial
oxidation of heavy residues using Lurgi’s Multi
Purpose Gasification Process in quench config-
uration at 6.0 MPa. The water-saturated raw gas
from the quench vessel enters the scrubber at ca.
240 ◦ C, where residual soot/ash traces are re-
moved by injection of additional quench water.
No further raw gas cooling occurs in the scrub-
ber. The water leaving the quench section con-
tains most of the soot and ash from the raw gas
and is further treated in the Metals Ash Recovery
System (see Section 3.2).
The raw gas from the MPG unit is saturated
with water and routed to the CO shift conversion
unit. After preheating of the raw gas, its CO con-
tent is reduced in a single-stage reactor to a resid-
ual 6 to 9 %, depending on the composition of
the feedstock. No further steam injection into the
shift feed is necessary to maintain the shift reac-
tion. The sensible heat of the shifted gas is reco-
vered by producing steam of different pressure
levels and by preheating several water streams
(quench water, demineralized water). The con-

Figure 85. Simplified process flow diagram for the gasification (quench configuration) and the CO shift section in Figure 84
densate from the cooled shift product gas is sent
to the MPG unit as quench and scrubbing water.
Both carbonyl and hydrogen sulfides are
washed out of the gas to a residual 1 ppm in a
one—stage Rectisol unit. The factors determin-
ing the selection of the Rectisol process instead
of a chemical absorption system are
– Low steam consumption,
– High selectivity for H2 S versus CO2 for the
generation of a rich acid gas to facilitate the
sulfur recovery.(see 5.4.2.4) for detailed dis-
cussion on acid-gas removal options).
The acid gas, which contains 25 – 60 % hy-
drogen sulfide, depending on the sulfur content
of the feedstock, is normally discharged to a cen-
tral Claus plant that also treats other sulfur con-
taining gas streams originating in the refinery to
produce elemental sulfur.
In the final purification of the raw hydrogen
in the pressure-swing adsorption unit CO2 and
other impurities are reduced to 10 ppm of carbon
dioxide, 10 ppm of carbon monoxide, and 0.1 %
(maximum) of inerts, yielding hydrogen with a
purity > 99.9 % (see Section 5.5) at a pressure
between 4.7 and 4.8 MPa.
Plant Performance. For easier comparison of
the improved concept with conventional process
routes, three cases are considered for the eco-
nomic evaluation:
Case 1: = MPG (quench) + single-stage raw
gas shift + H2 S absorption + PSA
Gas Production 147
Case 2: = MPG (quench) + two-stage raw gas
shift + acid gas absorption (H2 S, CO2 ) +
PSA (for remaining impurities only)
Case 3: = Texaco Gasification (TGP, quench) +
two-stage raw gas shift + acid gas absorp-
tion (H2 S, CO2 ) + PSA (based on [290],
scaled to hydrogen production without
power generation)
The characteristics of the respective plant
performance are summarized in Table 40.
To compensate for the lower H2 yield of the
MPG/single-stage CO shift process variant, the
plant capacity must be by 6 % higher which leads
to higher variable operating costs. On the other
hand the simple plant configuration of this route
results in lower capital costs and fewer main-
tenance costs and therefore reduced fixed costs
which makes this concept the most economical
one.
7.3. Combined Cycle Power System
Based on Coal
7.3.1. Introduction
Combined cycle power plants are an attractive
option to raise the efficiency of electric power
generation. This power plant concept combines
a gas turbine and a conventional steam turbine
148 Gas Production
Table 40. Performance of improved-concept plants for hydrogen production from heavy residue
Case 1 Case 2 Case 3
MPG, single-stage CO shift MPG, two-stage CO shift TGP [290]
Inputs SDA pitch (S: 5 wt %, ash: 0.07 SDA pitch (S: 5 wt %, ash: 0.07 Asphalted vacuum residue
wt %) wt %)
Feed oil, t/d 960 905 1050
Oxygen (99.5 %), t/d 925 875 1120
Process steam to gasifier, t/d 430 405 475
Intermediate products
Fuel gas from PSA (LHV, kJ/m3 (STP) > 4500 ca. 8000 ca. 1000
Acid gas from Rectisol unit (vol % H2 S)< 60 < 60 not available
Products
Hydrogen, t/d 188.4 188.4 218
Byproducts, t/d
Sulfur 47.8 45.1 58
Metals, ash 0.6 (76 wt % V2 O5 ) 0.56 (76 wt % V2 O5 ) 8.5 (filter cake, dry)
Steam export 1920 1810 2110 (calculated)

cycle. Based on available industrial gas turbines
early plant concepts were developed and intro-
duced in the early 1950s, these plants were fu-
eled by conventional oil-derived gas or almost
any kind of fuel gas. Although basic process con-
cepts are well established, novel concept varia-
tions are still under development [293].
Due to its relatively low price as well as re-
gional availability, coal is the major fuel for
fossil-fueled power plants. To use combined cy-
cle technology, coal must be transformed into
a clean fuel applicable to gas turbine operation
(the same applies to residual oil, petroleum coke,
or wood). Impurities, which must be removed,
are ash, alkali, halogens, and sulfur. Typical gas
turbine specifications are given below:
Inlet temperature, ◦ C (according to ISO) 1190
Na + K, mg/kg 0.08
V, mg/kg 0.1
Pb, mg/kg 0.25
C, mg/kg 2.5
Cl, mg/kg 2.45
Dust < 2 µm, mg/kg 4.4
The only way to meet these requirements is
gasification because
1) Ash remains in the gasification residue,
2) Alkali is trapped within the ash or removed in
one of the purification steps, and
3) Halogens and sulfur are removed by dry or
wet absorption.
The combined effect of high efficiency and
low pollution makes the combined cycle with
upstream coal gasification an attractive approach
for power generation from coal. In principle,
two designs are possible: integrated and nonin-
tegrated plants. In the latter, the gasification and
gas purification process units are installed and
operated separately from the power plant. This
makes power plant operation easier, but an in-
tegrated plant (IGCC) allows for more sophisti-
cated energy management and higher efficiency
[294]. Hence, most engineering and economic
studies and first-of-its-kind plants refer to this
design principle. In this section only the princi-
ples of the integrated combined cycle based on
the gasification of solid fuels are discussed [295,
296].
Environmental Aspects. The emissions of
combined power cycles are inherently lower
than that of coal combustion plants [297 – 299].
This is due mainly to the following characteris-
tics:
1) Desulfurization of the fuel gas can be accom-
plished to any extent necessary at a relatively
low additional cost. For applicable processes,
see Section 5.4.
2) The byproduct of desulfurization is elemental
sulfur, which can be sold or easily disposed
of, in contrast to flue gas scrubber residues.
3) Low NOx emissions are achievable due to the
tightly controllable combustion conditions in
a gas turbine.
4) Extensive particulate removal is essential for
gas turbine operation, resulting in dust emis-
sions far below existing requirements.
7.3.2. Fundamentals
Thermodynamics [300, 301]. Electric
power is conventionally generated by com-
bustion to produce high-temperature thermal

energy and converting that thermal energy into
work to drive a generator. The working fluid can
be the combustion gas itself or a special working
medium (steam, air) to which heat is transferred
from the combustion gas.
The upper limit to the proportion of thermal
energy converted to work is set by Carnot’s law
t2
η≈1−
t1
where t 1 and t 2 are the upper and the lower ab-
solute temperatures of the working fluid and η is
the conversion efficiency. For a steam turbine cy-
cle construction materials usually limit the upper
temperature to ca. 560 ◦ C, the lower temperature
depends on the available cooling water tempera-
ture. With sea water cooling lower temperatures
of ca. 30 ◦ C are achievable. For an open cycle
gas turbine (stationary application), t 1 may be
as high as 1050 ◦ C, with t 2 being ca. 500 ◦ C
depending on the pressure ratio.
When gas and steam turbines are combined
by using the thermal energy of the gas turbine
exhaust gas to produce and superheat the steam
from the steam cycle, t 1 may be as high as
1050 ◦ C and t 2 as low as 30 ◦ C. This, in simpli-
fied terms, is the basis for the efficiency increase
when a dual cycle combining gas and steam tur-
bines is used instead of a single working fluid
cycle. Some losses occur along the route from
coal to electrical energy. For simplification the
overall efficiency of the process can be written
as the product of individual efficiencies:
η = ηCG ·ηGC ·ηCC
where η CG is the efficiency of coal gasification;
η GC , the efficiency of gas cleaning; and η CC ,
the efficiency of the combined cycle.
Efficiency of Coal Gasification η CG . Coal
gasification processes suffer losses of useful en-
ergy due to the following mechanisms:
1) The heat of evaporation of gasification steam,
coal moisture or slurry water cannot be reco-
vered.
2) The bottom or fly ash inevitably contains un-
converted carbon which is lost for the process.
The same applies for the sensible heat of the
ash.
3) Heat is lost to the environment, e.g., through
the walls of apparatus and pipes.
Gas Production 149
4) The operation of drives, pumps and compres-
sors consumes electric energy, which can be
recovered only partly.
5) The gasification reactions require elevated
temperatures. During cleaning of the hot raw
gases, according to the requirements of the
gas turbine operation and of the environment,
the raw gas has to be cooled down by heat
exchange which involves a certain degree of
irreversibility.
Each of the mechanisms leads to a different
amount of losses for the individual gasification
processes. Reference figures for η GC may be
taken from Section 4.4, 4.5, 4.6, 4.7 (Tables 18,
20, 21, 23).
Efficiency of Gas Cleaning η GC . The
losses of useful energy during gas cleaning can
mainly be attributed to
1) Nonreversible heat exchange during cooling
of the raw gas and reheating of the clean gas,
2) The energy required for the regeneration of
the solvent or adsorbent, which in most in-
stances is lost,
3) The removal of sulfuric components and the
co-removal of other combustible constituents
of the raw gas which, therefore, cannot con-
tribute to the combined gas/steam turbine op-
eration,
4) The removal of inerts such as H2 O and CO2
which reduces the mass flow through the gas-
turbine and hence its energy output, and
5) The consumption of electric energy.
In most cases η GC reaches 96 – 98 %.
Efficiency of Combined Cycle ηCC . For
thermodynamic reasons the efficiency of the
conversion of thermal energy into work and con-
sequently electric power is limited as has been
explained earlier. In addition to that, other losses
of useful energy must be considered, e.g.:
1) The heat of evaporation of boiler feed water
is only partly used for generation of power.
2) The nonideal operation of gas and steam tur-
bines increases the entropy of the working flu-
ids.
3) The flue gases leave the stack with a tempera-
ture above 100 ◦ C, their thermal energy is not
used for the process.
4) Heat losses through the insulation.
150 Gas Production

Based on natural gas, a combined cycle with where dusty and tarry compounds are removed
a gas turbine inlet temperature of 1100 ◦ C (ac- from the gas. Simultaneously the gas is cooled to
cording to ISO) may reach 48 % efficiency [299, ca. 160 – 170 ◦ C and saturated with water. The
302]. dusty tar removed from the gas is recycled in to-
At a coal gasification efficiency of ca. 90 % a tal to the gasifiers after separation from the wash
combined cycle power generation unit based on water. The clean gas is passed through a first gas
coal gasification achieves an overall efficiency η turbine (e) which drives the booster compressor
> 42 %. (b) for the gasification air. Here the pressure of
the clean gas is reduced from 2 to ca. 1 MPa. A
General Plant Arrangement. In principle, bypass stream of 1 % of the clean gas is desul-
any high-pressure coal gasification process men- furized with a hot potassium wash solution for
tioned in Chapter 4 can be used as the front- pilot test purposes.
end process. The selection of a gasification pro-
cess depends on several boundary conditions,
the most important of which are
1) Type of available coal (rank, particle size, ash,
and moisture content);
2) Gasifier efficiency; and
3) Maturity of the process and its proven relia-
bility.
Coal gasification can be integrated with com-
bined cycle power generation in numerous ways.
Modifications differ in the degree of carbon con-
version (partial or total gasification), the gasi-
fication medium (air or oxygen), the measures
taken to adjust the turbine inlet temperature
(excess air or steam production), and the gen-
eral arrangement (stand-alone plant or repow-
ering). Advantages and limitations of the indi-
vidual variants are described in [294, 297], and
[303 – 307].

7.3.3. Installations and Design Studies

Installations. The first commercial-scale

IGCC plants have been built at Lünen by Steag in
the Federal Republic of Germany [308] and near
Barstow, California (The Cool Water plant). The
Lünen plant with a design output of 170 MW
operated between 1972 and 1977; the Cool Wa-
ter plant (100 MW) began operation in 1984. At
present both plants are no longer in operation.
Lünen IGC Plant. The general arrangement
of the Lünen plant is shown in Figure 86. Gasi-
fication takes place in 4 + 1 Lurgi moving bed
gasifiers (see Section 4.4). High volatile subbitu-
minous coal is gasified with steam and air coun-
tercurrently at a pressure of 2 MPa (c). The raw
gas leaves the gasifiers with a temperature of 500
– 600 ◦ C. It is cleaned in a scrubbing unit (d)
Figure 86. Simplified flow diagram of the IGCC Lünen
plant
a) Air compressor; b) Gasification air compressor; c) Lurgi
gasifiers (in all five); d) Wet gas cleaning; e) Expansion
turbine; f) Supercharged boilers (in all two); g) Gas tur-
bine; h), i) Boiler feed water preheaters; j) Steam turbine;
k) Condensor; l) Boiler feed water pump; m) Generator
The clean gas is combusted in two super-
charged boilers (f) at 1 MPa which is a partic-
ular feature of this plant. In these boilers 340 t/h
steam are generated (13 MPa, 525 ◦ C) power-
ing a steam turbine (j) with an output of 96 MW.

The flue gases leaving the supercharged boilers
drive a second gas turbine (g) with an output of
74 MW. The compressor for the total plant air
is connected to the same shaft. In the gas tur-
bine the flue gas enthalpy is reduced from 1.0
Pa, 810 ◦ C down to 0.1 MPa and 400 ◦ C. The
residual thermal energy of the exhaust gases is
used for boiler feed water heating (i, k), the stack
inlet temperature is 170 ◦ C [297, 309].
As a first-of-its-kind plant, the Lünen plant
did not operate continuously; altogether it pro-
duced electrical energy for the grid for ca. 10
000 h. During this time, the data in Table 41
were obtained.
Table 41. Performance data, in percent, of the Lünen plant at 70 %
partial load
Efficiency Partial load
Design Operation
Design Coal 1 * Coal 2 **
coal
η CG 91.7 90.2 86.1
η CC 35.8 35.2 35.0
η 32.8 31.7 30.5
* Coal 1 = design.
** Coal 2 = low grade (40 % < 5 mm, 28 % ash).
The plant generally operated at partial load
and with low-grade coal. Table 41 also shows
estimated full load design data which were not
achieved because only 70 % of the necessary
gasification air could be supplied due to limi-
tations in air compression.
The second commercial-scale installation is
the Cool Water plant [310, 311]. The plant is of
commercial size, with a net output of ca. 100
MW.
In this plant, a Texaco entrained-flow gasifier
(see Section 4.6) was used, which gasified a coal
– water slurry with oxygen. According to pre-
vailing emission standards, the gasification raw
gas was purified by a physical absorption pro-
cess (Selexol, see Section 5.4), which reduces
the content of carbonyl and hydrogen sulfide in
the purified gas to 50 ppm. Besides demonstrat-
ing the IGCC process principles the Cool Water
plant was used to test construction materials and
general control strategies.
Design Studies. The two plants have not
been designed to exploit the full potential of
IGCC. Their main purpose was the demonstra-
Gas Production 151
tion of the technical feasibility and operability
of plants of this kind.
Hence the overall efficiency of these early
IGCC plants is limited compared to modern
power stations based on the Rankine process.
The successful introduction of natural gas
fired IGCC plants stimulated numerous design
studies based on gasification of solid fuels.
Gasification processes which were considered
are the Lurgi fixed-bed gasification [297], the
British Gas/Lurgi slagging gasifier [304, 312,
313], entrained-flow gasification [304, 305], and
fluidized-bed gasification [305, 314 – 316]. De-
pending on constraints like available fuel qual-
ity and sophisticated heat recovery systems effi-
ciencies η  40 % can be expected.
100 % load The most recent commercial scale IGCC
Design power plants based on coal gasification have
Design coal
been commissioned at Buggenum (NL) (250
MW) by DEMKOLEC B.V. [317 – 319],
92.9 at Puertollano (Spain) (320 MW) [320];
39.4
and Tampa (USA) [322]. The DEMKOLEC
36.7
Buggenum plant applies entrained-flow gasifi-
cation for turbine fuel production; standard fuel
is conventional hard coal (ca. 2000 t/d). Com-
mercial operation started in 1994. In a single
train 250 MW of electric power are generated;
based on the experience gained so far, capac-
ities of 500 MW are regarded as feasible. The
block diagram (Fig. 87) depicts the main build-
ing blocks of a typical IGCC layout following
the DEMCOLEC design; Figure 88 presents an
aerial view of the total plant . A major part
of the setup is taken up by the gas cleaning
and desulfurization systems. A conventional
Claus – SCOT plant converts H2 S to elemental
sulfur. The IGCC plant at Puertollano uses an
entrained-flow gasifier to convert low grade sub-
bituminous coal into fuel gas for a gas turbine
[320, 321]. This project is jointly executed by
several companies of different European coun-
tries and funded by the European commission.
The Tampa IGCC plant was commissioned in
1996, using entrained-flow gasification; in ad-
dition to hard coal refinery residues can be used
for gasification [322].
Besides these plants in operation, numer-
ous studies investigated the suitability of IGCC
plants for a wide range of feedstocks [314, 316,
323]. IGCC concepts have also been investigated
with regard to the gasification of unconventional
fuels [319, 323 – 325]. The use of biomass de-
152 Gas Production
Figure 87. Principle layout of an IGCC plant
rived fuels opens the possibility for a reduction
of CO2 emissions whilst retaining high power
generating efficiencies.
Figure 88. Aerial view of the DEMKOLEC plant
8. Analysis and Quality Control
Fuel gases [336] are sold principally as a source
of energy, but in units described by volume. Con-
sequently, considerable demand exists for spec-
ification of the thermal content per unit volume.
The range of fuel gases that will burn satisfacto-
rily on a particular appliance is limited and best
described by the Wobbe index of the gas. The
Wobbe index is a measure of the heat input to an
appliance at constant pressure, and is expressed
as the ratio of the calorific value to the square
root of the relative density. This property should
also be specified. Safety requirements relate to
the flammable nature of the fuels, and engineer-
ing considerations relate to their distribution and
storage.
Specifications for fuel gases cover various
properties and may be devised or imposed by
different authorities. Requirements for the spec-
ification of and means of ensuring satisfactory
odorization are commonly a responsibility of
government. Control of Wobbe index and of par-
ticular components that may have operational
implications, such as water and condensable
hydrocarbons, are usually the responsibility of
the supply and distribution company. Different
countries have different specifications [337], al-
though common interests ensure a degree of con-
sistency.
If a fuel gas is to be used as a chemical feed-
stock, quite different specifications will be used;
total carbon content and the quantity and types
of sulfur compounds present might be of much
greater importance.
8.1. Quality Specifications
Natural gas supplies by far the greater part of
the fuel gas market. The quality specifications
 Gas Production 153
Table 42. Classification of fuel gases according to gas family (DVGW a Rule G 260) [340]
Symbol Unit First Family (town gas) Second family (natural gas) Third family
(LPG)
Group A Group B Group L b Group H c
Wobbe index Ws
Total range MJ/m3 23.0 – 28.1 28.1 – 33.5 37.8 – 46.8 46.1 – 56.5 requirements
(STP) for
Nominal range MJ/m3 44.6 54.0 propane and
(STP)
Range of variation in W s MJ/m3 + 0.6 to − 1.4 + 0.7 to − 1.4 propane –
location distribution (STP) butane
mixtures (≥ 60
wt %
Gross calorific value Hs C4
hydrocarbons)
Total range MJ/m3 16.6 – 19.8 18.0 – 21.2 according to
(STP) DIN
Nominal range MJ/m3 17.6 19.8 51 622
(STP)
Range of variation in H s MJ/m3 ± 0.3 ± 0.3
location distribution (STP)
Relative density d 0.40 – 0.60 0.32 – 0.55 0.55 – 0.704
Appliance inlet pressurepe
Total range kPa 0.75 – 1.5 0.75 – 1.5 1.8 – 2.4 4.25 – 5.75
Nominal range kPa 0.8 0.8 2.0 5.0
a
DVGW = Deutscher Verein des Gas- und Wasserfaches e.V.
b
L = low.
c
H = high.

Table 43. Recommended limits of gas impurities according to

of natural gas have been reviewed in both Euro- DVGW * Rule G 260 [340]
pean and North American contexts [338, 339].
Gas family
First Second
Benzene hydrocarbons,
8.1.1. Combustion Characteristics g/m3 (STP) 10
Naphthalene, mg/m3 (STP) 50/p (p in bar)
Fuel gases are categorized in one of three fami- Hydrocarbon dew point, ◦ C soil temperature at
Water dew point, ◦ C pipeline pressure
lies: (1) manufactured gas (high hydrogen con- Fog, dust, liquids technically pure
tent), (2) natural gas and (3) liquefied petroleum O2 (dry distribution grid),
gas [340]. Table 42 shows these families and the vol % 3 3
O2 (wet distribution grid), vol % 0.5 0.5
subdivisions for manufactured and natural gas,
NO, cm3 /m3 (STP) 0.2
within which interchangeability [341, 342] may Total sulfur, mg/m3 (STP) 200 120
be assumed. Test gases for evaluation of appli- Short-term value,
ances within these families are described [343]. mg/m3 (STP) 150
Mercaptan sulfur, mg/m3 (STP) 6
Other combustion properties are flame lift Short-term value, mg/m3 (STP) 16
[344 – 346], incomplete combustion (yellow tip- H2 S, mg/m3 (STP) 2 5
ping) and flashback [347]. Short-term value, mg/m3 (STP) 10
NH3 , mg/m3 (STP) 3
CN, mg/m3 (STP) 150
CO, vol % 6
8.1.2. Minor Constituents * DVGW = Deutscher Verein des Gas- und Wasserfaches e.V.

Specifications from several (mainly European)

countries have been compared [337]. Typical na-
tional requirements for maximum levels of im-
purities (Table 43) [340] and odorization [348]
are described.
154 Gas Production
8.2. Test Methods
8.2.1. Determination of Combustion
Characteristics
8.2.1.1. Calorimetry
The calorific value (heating value) H of a fuel
gas is defined as the amount of heat released by
complete combustion in air, at constant pressure
p1 , with the combustion products being returned
to the same temperature t 1 as that of the reac-
tants prior to combustion. Normally the superior
calorific value H S (synonymous higher heat-
ing value, HHV) is experimentally determined
with all the water formed by combustion being
condensed to the liquid state at t 1 . The inferior
calorific value H I (synonymous lower heating
value, LHV) is defined as the amount of heat
released with all the water formed remaining in
the vapor phase at t 1 and p1 .
The calorific value H can be measured or in-
ferred in three ways: (1) direct combustion with
measurement of heat released, (2) stoichiomet-
ric combustion with measurement of gas – air
ratio, and (3) calculation from composition.
Direct Measurement. The calorific value
can be measured directly in a reference
calorimeter, in which the heat liberated from a
discrete amount of gas is measured thermometri-
cally [349]. More frequently, however, continu-
ous recording calorimeters are used [350 – 354].
The principle of continuous recording calorime-
ters is combustion of a controlled stream of gas,
followed by heat exchange of the products of
combustion with another fluid, whose tempera-
ture rise is recorded.
Stoichiometric Combustion. Stoichiomet-
ric combustion relies upon the constancy of the
ratio of calorific value to air – gas ratio for sat-
urated hydrocarbons. For this reason, it can be
used for natural gas, but not manufactured gas
[355]. Stoichiometric combustion devices have
been used as part of an energy flow meter [356],
where the rate of supply of gas to the meter is
kept exactly proportional to the flow in the main
stream from which it is taken.
Calculation from Composition. The com-
position of fuel gases can be defined very well
by gas chromatographic measurement. Knowl-
edge of calorific values for the pure components
and an appropriate calculation routine [357, 358]
lead to the calorific values H S and H I of the mix-
ture.
8.2.1.2. Density
Gas Density Balance. The gas density
(mass per unit volume) or relative density d (ra-
tio of the density of the fuel gas to the density of
dry air) [359] is most commonly determined by
a gas density balance [360, 361]. The method is
based on the buoyancy of a nitrogen-filled sphere
in the test gas. Instruments of this type also allow
continuous monitoring of gas density.
Oscillating Device. Another method for de-
termining density employs an oscillating device
(e.g., a tuning fork). The frequency of oscillation
is a function of the density of the gas surrounding
it [362].
Both types of density recorders are checked
and calibrated by standard gas mixtures of
known (e.g., gravimetrically determined) den-
sity [363]. Density and relative density may also
be calculated from gas analysis [357].
8.2.1.3. Wobbe Index
The Wobbe index W is defined as the ratio of
calorific value H to the square root of relative
density at the same specified metering reference
conditions. As with the calorific value it must
be distinguished between superior Wobbe index
W S and inferior Wobbe index W I . Normally, the
Wobbe index W is not measured directly, al-
though it is one of the most important combus-
tion characteristics for describing gas quality.
Calculation of Wobbe Index. The index
can be calculated from the calorific value and the
relative density more accurately than by direct
determination. The Wobbe index may also be
obtained by combining the signals of a calorime-
ter and a densimeter electronically, according to
its definition equation.

Direct Measurement of Wobbe Index. Di-
rect measurement of the Wobbe index with rel-
atively simple and rapid instruments is recom-
mended only for mixing gases of different qual-
ity to yield a mixture of constant Wobbe index.
These Wobbe recorders are automatic calorime-
ters whose gas flow √ rate is adjusted so that it is
proportional to 1/ d.
8.2.2. Analytical Methods
The analytical methods listed in the follow-
ing sections are (1) general methods (i.e., ca-
pable of measuring several components, Sec-
tion 8.2.2.1); (2) specific methods for individual
components (Section 8.2.2.2); or (3) methods
suitable for minor components (Section 8.2.2.3).
Sampling is the first, and a most impor-
tant, stage in gas analysis. Therefore, great care
should be taken to obtain representative sam-
ples for determining gas properties and com-
position [364]. Continuous automatic sampling
techniques have also been developed [365].
8.2.2.1. General Methods for Determination
of Several Components
, etc.) [357, 358].
Orsat Method. The main constituents of manu-
factured gases (CO2 , O2 , CO, unsaturated hy-
drocarbons, H2 , saturated hydrocarbons and N2 )
were determined volumetrically by the classic
Orsat method involving successive absorption
of the constituents in specific reagents and se-
lective combustion of hydrogen and saturated
hydrocarbons [366]. A simplified Orsat appara-
tus is used at present only for flue gas analysis or
in combination with the chromatographic Janak
method for carbon dioxide, oxygen, and unsat-
urated hydrocarbons.
Janak Method. The Janak procedure, which
is suitable for manufactured gases as well as for
natural gas components up to C4 H10 , is a simple
chromatographic method using carbon dioxide
as carrier gas [367]. The carrier gas emerging
from the column passes to a burette filled with
concentrated potassium hydroxide solution, in
which carbon dioxide is absorbed and the re-
maining components can be measured consecu-
tively by volume. The apparatus available com-
mercially registers the volume ratio of the dif-
ferent components with an automatic burette.
Gas Production 155
Gas Chromatography (GC). Besides the
Janak method, GC [368 – 370] with a ther-
mal conductivity or flame ionization detector
is most often recommended for fuel gas anal-
ysis. A large number of standardized methods
exist for the analysis of manufactured gas [371]
and natural gas [372 – 374] by using an ad-
sorption column (e.g., molecular sieve) for the
separation of hydrogen, helium, oxygen, argon,
nitrogen, methane, and carbon monoxide, and a
partition column (e.g., organic stationary phase
on a solid support) for the separation of higher
hydrocarbons. For the analysis of natural gas,
determination of hydrocarbons up to pentane
[372] or octane [373, 374] is normally suffi-
cient. For specific needs, methods have been
developed for analysis up to hexadecane [375].
For onstream applications, these analyses
have been completely automated (process GC):
this includes periodic calibration of the total sys-
tem with a calibration gas mixture [376] and
evaluation of the chromatogram by an electronic
integrator. Gas analyses can also be performed
by mass spectrometry [377]. The results of these
analyses can be used to calculate the physical,
thermodynamic, and combustion characteristics
of the gas (H S , H I , W S , W I ,
8.2.2.2. Specific Methods for Determination
of Individual Components
Hydrogen. In binary or quasibinary gas mix-
tures, the hydrogen content can be monitored
easily by measuring thermal conductivity, be-
cause the conductivity of hydrogen is much
higher than that of all other likely components.
Oxygen. Besides volumetric [366], chemical
[378], and GC methods [373], oxygen (concen-
tration >0.1 vol %) may be determined without
significant interference from other components
by using instruments based on the measurement
of magnetic susceptibility [379].
Carbon Dioxide. The carbon dioxide con-
centration [380] of fuel and flue gases is nor-
mally recorded by nondispersive infrared instru-
ments [381, 382]. The carbon dioxide absorption
band is overlapped only slightly by the carbon
156 Gas Production
monoxide band, and for a wide range of concen-
tration ratios this interference can be eliminated
by using a filter cell containing carbon monox-
ide. Several instruments are available that use
single- or double-beam techniques and different
types of detectors. For discontinuous determi-
nation, aforementioned volumetric [366] or GC
methods [371, 373] may be used.
Carbon Monoxide. Infrared absorption is
also the recommended method for monitoring
the carbon monoxide concentration of gases
[383]. Interference from carbon dioxide must be
filtered out in the manner described above. Gas
chromatography [384] and detector tubes [385]
may be used for consecutive measurements or
for a single check. Carbon monoxide detector
tubes are subject to interference from propane
and higher hydrocarbons, which may be found in
natural gas. This interference can be eliminated
by first leading the gas through an adsorption
tube filled with activated carbon.
8.2.2.3. Methods for Determination of
Minor Components
Water Content. For discontinuous gravi-
metric determination of water, a drying tube
containing a suitable desiccant (e.g., magnesium
perchlorate) can be used [386]. Alcohols such
as methanol or glycols are also absorbed. Water
and methanol (concentration > 20 mg/m3 ) can
be determined by GC [387].
The Karl Fischer method [388], in which wa-
ter reacts with iodine in an alcoholic solution of
sulfur dioxide and pyridine, is suitable for the de-
termination of low water content of the order of
milligrams per cubic meter. Newer equipment in
which iodine is generated coulometrically [389]
is particularly suitable for this application.
A variety of hygrometers use different detec-
tors [390, 391], such as electrolytic cells with
phosphorus pentoxide as absorbent, conductiv-
ity cells with glycerol [392], a capacitor with
aluminum oxide as the moisture-sensitive di-
electric medium [393], silicon chips, and an os-
cillating quartz crystal. By absorption or adsorp-
tion of water from the surrounding gas, the elec-
trolytic current, conductivity, dielectric proper-
ties, or frequency of oscillation is changed. Bet-
ter instruments use a sophisticated purge and cal-
ibration technique to overcome contamination
problems caused by hydrocarbon condensates
and other impurities such as glycols or etha-
nolamines derived from gas treatment processes
[394]. Some of these instruments measure water
content in parts per million (mL/m3 or mg/m3 );
others indicate dew point temperature.
Although water content and dew point can be
related theoretically, some uncertainty exists as
to whether this can be applied with any degree of
accuracy to uel gases. Measurement from any in-
strument is more safely related to the technique
used for calibration.
Water Dew Point. Because of the risk of hy-
drate formation [395], gas temperature should
not drop below the dew point. The water dew
point can be determined directly when a constant
stream of gas passes over a polished metal mirror
that is cooled slowly [396]. The dew point corre-
sponds to the temperature at which the first signs
of condensation appear on the mirror. The mea-
surement can be performed under pressures up
to 10 MPa. Completely automated instruments
employing photocells are also used [390]. If the
gas contains methanol or glycols, the dew point
corresponds to the simultaneous condensation
of water and alcohol. If the methanol content is
known, a correction can be applied to the ob-
served dew point [396]. Condensation of hy-
drocarbons may also interfere, when the hydro-
carbon dew point is higher than that of water.
This interference can be reduced significantly by
first passing the gas through high-boiling liquid
paraffin.
Sulfur Compounds.
Total Sulfur. The combustion method is ap-
plicable to all fuel gases. A measured volume of
gas is burned with excess air or oxygen in a spe-
cially designed apparatus (e.g., Wickbold [397],
lamp [398], Lingener method [399]). Combus-
tion products are absorbed in an oxidizing solu-
tion. The sulfuric acid formed is determined by
volumetric, gravimetric, or turbidimetric meth-
ods [400]. Sulfur dioxide can also be titrated
coulometrically [401].
In the hydrogenation method, sulfur com-
pounds are catalytically hydrogenated to hydro-
gen sulfide at high temperature over platinum
gauze in the presence of excess hydrogen and

water vapor. Subsequent determination of hy-
drogen sulfide by the methylene blue procedure
is very sensitive [402]. The lead acetate paper
method in combination with hydrogenation is
less precise but can be automated for continu-
ous photometric recording [403].
Simultaneous Determination of Hydrogen
Sulfide, Carbonyl Sulfide, and Mercaptan Sul-
fur. A measured volume of gas is passed through
two sets of bubblers in series. The first set con-
tains concentrated potassium hydroxide solution
in which hydrogen sulfide and mercaptans are
absorbed; the second contains alcoholic mono-
ethanolamine solution, which absorbs carbonyl
sulfide. Potentiometric titration with silver ni-
trate measures each species [404].
Individual Sulfur Compounds. The preferred
method for determining individual organic and
inorganic sulfur compounds is GC. Although
sulfur compounds can be detected by ther-
mal conductivity or flame ionization detectors
(the latter for organic sulfur compounds only),
sulfur-specific detectors are preferred for the
analysis of naturally occurring or added odor-
iferous sulfur compounds to avoid interference
from other components. The flame photometric
detector [368, 405] measures the light emitted
at 396 nm when sulfur compounds are burned in
a hydrogen-rich flame.
The electrochemical detector widely used for
the control of gas odorization registers the po-
tential change of an electrolytic cell when chro-
matographically separated sulfur compounds
are oxidized by concentrated chromium triox-
ide solution [406]. Carbonyl sulfide, which is not
indicated by this detector in its normal mode of
operation, may also be detected when potassium
hydroxide solution is used instead of chromium
trioxide.
The Hall detector measures the change in
conductivity caused by absorption of sulfur
dioxide in an electrolyte after the effluent of the
chromatographic column has been burned with
excess oxygen by passing the gas stream through
a narrow nickel tube at high temperature [407].
The change in conductivity is directly propor-
tional to the sulfur content of the effluent. The
same principle has also been used for monitoring
the total sulfur content of fuel gases.
Hydrogen sulfide can be determined by the
formation of brown or black stains of lead sul-
fide on lead acetate paper. This can be a simple
Gas Production 157
semiquantitative test, a manual quantitative de-
termination [408], or a completely automated
control [403]. For spot measurements, detector
tubes [385] may also be sufficient. Wet chemi-
cal determinations are based on iodometric titra-
tion [409] or the very sensitive Methylene Blue
method [410]. The coulometric method uses the
oxidation of hydrogen sulfide by electrochemi-
cally generated bromine. Interference from other
oxidizable sulfur compounds can be eliminated
by using a difference method with selective ab-
sorption solutions (e.g., CdSO4 for H2 S and
KOH for H2 S and mercaptans) [411]. Specific
electrochemical cells are used for monitoring
the hydrogen sulfide concentration in air or fuel
gases.
Carbon disulfide is normally determined by
GC [368], but colorimetric methods and detector
tubes [385] may also be used.
Besides the aforementioned GC and poten-
tiometric methods, carbonyl sulfide can be hy-
drolyzed in dilute potassium hydroxide solution.
The resulting sulfide is determined colorimetri-
cally by the Methylene Blue method.
Nitrogen Compounds.
Ammonia. Ammonia in manufactured gas is
determined by absorption in standard sulfuric
acid and titration of the excess acid [412]. Low
concentrations are indicated by reaction with
Nessler’s reagent, which is also used for colori-
metric determination. For spot measurements,
gas detector tubes are available [385].
Hydrogen Cyanide. Hydrogen cyanide in
coal gas with low hydrogen sulfide content can
be determined after absorption in a nickel –
sodium carbonate suspension [413] or in an am-
moniacal solution of zinc sulfate by titration
with silver nitrate. Gases with a higher con-
tent of hydrogen sulfide can be analyzed by the
cyanogen bromide method [414].
Nitrogen Oxides. Nitrogen dioxide forms a
red dye with Saltzman solution [415]. Nitric ox-
ide present in coal gas, therefore, must first be
oxidized by passing the gas through a sodium
permanganate solution. Both oxides can be de-
termined together, or nitric oxide alone, after se-
lective absorption of nitrogen dioxide.
For the analysis of flue gases, the chemilumi-
nescent reaction between nitric oxide and ozone
is used for NOx determination. If nitrogen diox-
ide is included, the gas must pass through a con-
158 Gas Production
verter where nitrogen dioxide thermally decom-
poses to nitric oxide and oxygen [416].
Condensable Hydrocarbons. Natural or
manufactured gases may contain amounts of
condensable hydrocarbons that can cause prob-
lems by forming gas condensates. In dry gas,
the hydrocarbon dew point may be determined
by the mirror method [396]. The potential hy-
drocarbon liquid content in natural gas can be
evaluated either by weighing or volumetrically
[417].
Gas benzene (i.e., BTX aromatics and higher
boiling hydrocarbons) was formerly determined
by adsorption on activated carbon and subse-
quent displacement by steam. Today, chromato-
graphic methods are preferred.
Naphthalene and other condensed aromatic
components can be determined chromatograph-
ically or in total by precipitation of the corre-
sponding picrates [418].
8.2.2.4. Determination of Trace Constituents
For the determination of trace constituent (e.g.,
nickel and iron carbonyl, chlorine [419], and
mercury [420]), several methods have been de-
veloped, using atomic absorption spectrometry
(AAS) to determine heavy metals.
9. Acknowledgement
The entire topic was coordinated by Gerhard
Hochgesand.
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389. ISO 10101, Part 1–3-1987; DIN 51869, ed.
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390. M. A. Berliner: Feuchtemessung, VEB Verlag
Technik, Berlin-Ost 1980.
391. A. W. Jamieson, H. J. Sikkenga in [331], pp.
289 – 299.
392. J. Rötter in [331], pp. 311 – 325.
393. P. L. Cremonesi in [331], pp. 301 – 310.
394. M. Mathews, Erdöl Kohle, Erdgas, Petrochem.
37 (1984) 95 – 96.
C. B. Blakemore, J. C. Steichen, G. Dallas in
[331], pp. 327 – 335.
395. DVGW-Regelwerk: Arbeitsblatt G 285,
Hydratinhibierung in Erdgasen mit Methanol,
ZfGW-Verlag, Frankfurt 1974.
396. ISO 6327- 1981.
AFNOR NF X 20–521, ed. Dec. 1981.
ASTM D 1142- 95.
BS 3156 Part 10.3. DIN 51871, ed. Dec. 1985.
397. ISO 4260- 1987.
DIN-EN 24260, ed. May 1994.
398. ASTM D 1072–90.
399. ISO 6326 Part 5–1989; DIN 51400 Part 4, ed.
Oct. 1990.
400. DIN 51400 Part 1, ed. Dec. 1992,
DIN 51400 Part 2, ed. Feb. 1978.
401. ASTM D 3246–92.
DIN 51400 Part 7, ed. June 1992.
402. ASTM D 4468- 85.
403. L. Below, GWF Gas Wasserfach Gas/Erdgas
120 (1979) 59 – 65.

404. ISO 6326, Part 3- 1989.
DIN 51855 Part 6, ed. March 1989.
405. P. A. Gibbons, Chromatographia 19 (1984)
254 – 256.
ISO 6326 Part 4- 1994.
DIN 51855 Part 8, ed. 1997.
406. ISO 6326 Part 2- 1981.
AFNOR NF X 20–511, ed. Jan. 1982.
DIN 51855 Part 7, ed. Dec. 1986.
407. C. A. Risk, R. A. Hall, J. Chromatogr. Sci. 15
(1977) 156 – 159.
DIN 51855 Part 8, ed. 1997.
408. ASTM D 2420–91.
ASTM D 4084–94.
DIN 51855 Part 3, ed. June 1979, withdrawn
1991.
409. ASTM D 2385–81.
DIN 51855 Part 4, ed. June 1995.
I. P. 103/70.
Gas Production 169
410. ASTM D 2725–87.
DIN 51855 Part 4, ed. June 1995.
411. G. Herbst, A. Romanski, GWF Gas
Wasserfach Gas/Erdgas 121 (1980) 105 – 108.
412. DIN 51854, ed. Sept. 1993.
413. DIN 51863 Part 1, ed. Sept. 1983.
414. DIN 51863 Part 2, ed. Sept. 1983.
415. DIN 51864, ed. Sept. 1986.
416. AFNOR NF X 43–018, ed. March 1983.
Verein Deutscher Ingenieure: VDI-Handbuch
Reinhaltung der Luft 2456, Part 5 + 6., ed.
May 1978.
417. ISO 6570 Part 1 – 3 1983/84.
DIN 51859, ed. June 1990.
BS 3156 Part 11.2.
418. DIN 51862, ed. Sept. 1982.
419. DIN 51408 Part 1, ed. June 1983.
420. W. Lommerzheim, GWF Gas Wasserfach
Gas/Erdgas 117 (1976) 430 – 432.
 Gelatin 1

Gelatin
Wilfried Babel, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Dieter Schulz, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Monika Giesen-Wiese, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Uwe Seybold, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Herbert Gareis, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Eberhard Dick, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Reinhard Schrieber, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Annelore Schott, Deutsche Gelatine-Fabriken Stoess AG, Eberbach, Federal Republic of Germany
Winfried Stein, Fritz Häcker GmbH & Co., Vaihingen/Enz, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 4.2. Food Industry . . . . . . . . . . . . . . 9

2. Structure and Properties . . . . . . . 2 4.3. Pharmaceuticals . . . . . . . . . . . . . 11
2.1. Structure . . . . . . . . . . . . . . . . . 2 4.4. Cosmetics . . . . . . . . . . . . . . . . . 12
2.2. Physical Properties . . . . . . . . . . . 4 4.5. Photography . . . . . . . . . . . . . . . 12
2.3. Chemical Properties . . . . . . . . . . 6 4.6. Technical Gelatin and Glue . . . . . 13
2.4. Microbiological Analysis . . . . . . . 6 4.6.1. Matches . . . . . . . . . . . . . . . . . . . 13
2.5. Quality Specifications . . . . . . . . . 6 4.6.2. Coated Abrasives . . . . . . . . . . . . . 13
3. Raw Materials and Production . . . 7 4.6.3. Paper Sizing . . . . . . . . . . . . . . . . 14
3.1. Raw Materials . . . . . . . . . . . . . . 7 4.6.4. Adhesives . . . . . . . . . . . . . . . . . 14
3.2. Production . . . . . . . . . . . . . . . . 7 4.6.5. Other Uses . . . . . . . . . . . . . . . . . 14
4. Uses . . . . . . . . . . . . . . . . . . . . . 9 5. Economic Aspects . . . . . . . . . . . . 14
4.1. General Aspects . . . . . . . . . . . . . 9 6. References . . . . . . . . . . . . . . . . . 15

1. Introduction the primary structure of collagen still exists in

Gelatin is a mixture of high molecular mass
polypeptides produced from collagenous animal
tissues such as hide splits, pigskin, and bones.
Collagen is the most commonly occurring pro-
tein in the human and animal body, account-
ing for about 30 % of the total protein content.
Since animal horns and hoofs are not composed
of collagen they cannot serve as raw materials,
contrary to popular belief. The name gelatin has
been used since about 1700 and is derived from
the Latin gelatus which means frozen [1]. There
is evidence that gelatin has been used for at least
4000 years [2]. The great variety of applications
of gelatin depend on its solubility in hot water, its
availability in a wide range of qualities, and its
ability to form thermally reversible gels, which
is unique for a protein and is due to the fact that
collagen-derived polypeptides.
2. Structure and Properties
2.1. Structure
Collagen is not a uniform substance but an entire
protein family. To date, some 19 polymorphs of
collagen have been identified. All types of colla-
gen have a triple-helix structure in which three
protein chains are intertwined to form a rigid
strand (Fig. 1). The length of the triple helix and
the type and position of the nonhelical regions
vary from one collagen type to an other.
The “classical” type I collagen, the most im-
portant type in the manufacture of gelatin, occurs

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 307
2 Gelatin
in skin and bone. Type II collagen occurs almost
exclusively in cartilage tissue, and type III col-
lagen occurs besides type I in skin. The concen-
tration of type III collagen is strongly dependent
on age: embryonic skin can contain up to 50 %,
but older skin only 5 – 10 %. The other collagen
types occur only in low concentrations and fulfil
mostly organ-specific functions.
Collagen consists of three helical polypep-
tide chains wound around each other and con-
nected by intermolecular cross-links. The triple
helix is formed intercellularly from three indi-
vidual chains (α-chains). Chain selection occurs
via intra- and intermolecular disulfide bridges
in the region of the N- and C-terminal pep-
tides, additionally supported by glycopeptide
structural elements. While collagen types II
and III contains three identical chains (ho-
motrimer [α1 (II)]3 ), type I collagen consists of
two identical and one somewhat differing chain
(heterotrimer [α1 (I)]2 α2 (I)). The triple helix
molecule is 300 nm long and 1.4 nm in cross sec-
tion. The amino acid sequences of the α1 and α2
chains are highly homologous (ca. 90 % corre-
spondence).
Collagen contains large amounts of two un-
usual amino acids: 4-hydroxyproline and ε-
hydroxylysine, which are the result of post-
translational modification: special enzyme sys-
tems facilitate the intracellular hydroxylation
of proline and lysine on the growing collagen
chain. Other enzymes are responsible for the gly-
cosylation of individual hydroxylysine residues.
Type I collagen, for example, contains 0.5 wt %
carbohydrate, and type III about 10 %. The car-
bohydrate portion comprises galactose and a
1,2-linked galactose – glucose disaccharide. The
ether-like bond between collagen and the sac-
charide occurs between the C1 atom of galactose
and the ε-hydroxyl group of hydroxylysine.
The enzyme-catalyzed modification steps
(hydroxylation and glycolyzation) are restricted
to growing individual chains; as soon as triple-
helix formation is initiated, modification ceases.
As stability of the helix is dependent on the hy-
droxyproline content, helix formation and pro-
line hydroxylation are interdependent and self-
regulating.
The helical part of all three collagen types
contains 1014 amino acids per chain, and the
N- and C-terminal nonhelical extension peptides
(telopeptides) are between 9 and 26 amino acids
long. The triple helix molecule has a molecular
weight of about 290 000, including the short N-
and C-terminal globular extension peptides.
Collagen consists of one-third glycine and
22 % of the imino compounds proline and hy-
droxyproline; the remaining 45 % comprises
some 17 other amino acids (Table 1). The con-
tent of acidic and basic amino acids is rela-
tively high. About one-third of the acidic ami-
no acids glutamic acid and aspartic acid is
present in the amidated form as glutamine and
asparagine. Cysteine is completely absent, and
of the sulfur-containing amino acids only me-
thionine is present at low concentration (excep-
tion: type III which has two cysteine residues
per 1000 amino acids).
The “classical collagen” types are character-
ized by repetitive tripeptide units – (glycine-X-
Y-)n – where proline occurs in the X and Y
positions and 4-hydroxyproline exclusively in
the Y position. Several other amino acids also
have preferred positions, presumably for steric
reasons. For example, glutamic acid, phenylala-
nine, and leucine occur frequently in the X po-
sition, and arginine mostly in the Y position.
Generally, collagen types from different species
are to a high degree homologous (usually about
90 %); and, within the same species, type I colla-
gen from skin, bones, and tendons are identical.
Triple-helix, water-soluble collagen (types
I to III) is converted extracellularly by cross-
linking and fibril formation into highly associ-
ated, water-insoluble collagen. These intra- and
inter-molecular cross-links are responsible for
a dramatic increase in stability of the collagen
molecule relative to thermal, mechanical, and
enzymatic influence. The type and extent of the
covalent cross-links are age-dependent, an as-
pect that is of considerable importance for the
gelatin industry. Process parameters and extrac-
tion conditions must hence be adapted to the age
of the raw materials (e.g., young pig or calf skin
/ old cattle hide).
2.2. Physical Properties
Commercial gelatin is a vitreous solid with a
faint color; it is almost tasteless and odorless
and usually contains 9 – 13 % moisture. It gives
typical protein reactions and is hydrolyzed by
 Gelatin 3

Figure 1. Schematic representation of the triple helix

Table 1. Comparison of the amino acid composition of collagen and gelatin: number of amino acids per 1000 (rounded off)

Amino acid Type I collagen (bovine) Type A gelatin ∗ Type B gelatin ∗∗

Alanine 114 112 117

Arginine 51 49 48
Aspargine 16 16 -
Aspartic acid 29 29 46
Glutamine 48 48 -
Glutamic acid 25 25 72
Glycine 332 330 335
Histidine 4 4 4
4-Hydroxyproline 104 91 93
ε-Hydroxylysine 5 6 4
Isoleucine 11 10 11
Leucine 24 24 24
Lysine 28 27 28
Methionine 6 4 4
Phenylalanine 13 14 14
Proline 115 132 124
Serine 35 35 33
Threonine 17 18 18
Tyrosine 4 3 1
Valine 22 26 22

∗ Type A gelatin: acid-pretreated pigskin gelatin. ∗∗ Type B gelatin: alkali-pretreated bone gelatin [1]

most proteolytic enzymes to give its peptide or
amino acid components.
Depending on the degree of hydrolysis, two
different types of gelatin are obtained:
1) Gelatin, gelling type [9000-70-8]: When the
granules are immersed in cold water they are
hydrated to discrete swollen particles. On
heating, these swollen particles dissolve to
form a solution.
2) Gelatin hydrolysate (also known as collagen
hydrolysate), nongelling type [68410-45-7]:
In this product range the molecular mass is
reduced to such an extent (< 15000 D) that
no gelation is observed. This type, mostly
produced as a fine powder is soluble in cold
water. Gelatin and gelatin hydrolysate are in-
4 Gelatin
soluble in less polar organic solvents such as
benzene, petroleum ether, ethanol, acetone
and tetrachloromethane.
Gelatin and gelatin hydrolysate are insolu-
ble in less polar organic solvents such as
benzene, petroleum ether, ethanol, acetone
and tetrachloromethane. Gelatin is ampho-
teric: in acidic solution gelatin is positively
charged and migrates as a cation in an elec-
tric field; in alkaline solution it is negatively
charged and migrates as an anion. The inter-
mediate point, where the net charge is zero
and no migration occurs, is known as the
isoionic or isoelectric point. Type A gelatin,
produced by acidic processing of collage-
nous raw materials, has a broad isoelec-
tric region between pH 6.0 and 9.5. Type B
gelatin, produced by the alkaline processing
of collagenous raw materials, has an isoelec-
tric point between pH 4.7 and 5.6. The dif-
ference in the isoelectric points of type A
and type B gelatins is the result of partial
desamidation of glutamine and asparagine
to the corresponding glutamic acid and as-
partic acid. Mixtures of type A and B, as
well as gelatins produced by modifications
of the above-mentioned processes, may ex-
hibit isoelectric points outside these ranges.
Gelatin in solutions containing no ions other
than H+ and OH− is known as isoionic
gelatin [3]. These solutions can be readily
prepared by the use of ion-exchange resins.
One of the most important properties of
gelatin (gelling type) is the formation of heat-
reversible gels in water. Gelatin readily forms
gels over a wide range of pH with a variety of
solutes. The formation and stability of a gelatin
gel is influenced by a number of factors. When
an aqueous solution of gelatin with a concen-
tration greater than ca. 1 % is cooled to about
35 – 40 ◦ C it first increases in viscosity and on
further cooling it forms a gel. The strength of
the gel depends on concentration and the intrin-
sic strength of gelatin used, which is a function
of structure and molecular mass. Gel formation
is not fully understood, but is believed to result
from hydrogen bonding; the gelatin molecules
are arranged in micelles that form a semisolid
gel and bind water. Quantitative measurement of
this property is important, both for control and
to determine the amount of gelatin required for
a given purpose because gelatin is used in many
products for its gel-forming properties. Modern
theory proposes that the first step in gelation is
the formation of locally ordered regions caused
by the partial random return (renaturation) of
gelatin to collagen-like helices (collagen fold).
Next, a continuous fibrillar three-dimensional
network of fringed micelles forms throughout
the system, probably due to nonspecific bond
formation between the more ordered segments
of the chains. Hydrophobic, hydrogen, and elec-
trostatic bonds may be involved in cross-linking.
Since these bonds are disrupted on heating, the
gel is thermoreversible. Formation of cross-links
is the slowest part of the process, so that under
ideal conditions the strength of the gel increases
with time as more cross-links are formed. The
total effect is a time-dependent increase in aver-
age molecular mass and in order. Renaturation
involves association between components (pep-
tide chains) that differ in degree of cross-linking,
chain length, and chemical composition [4], [5].
Gelatin is stable for long periods of time when
suitably stored in sealed containers, at normal
ambient temperatures to prevent ingress or loss
of moisture. When gelatin is heated above 45 ◦ C
in air at relatively high humidity it may lose its
ability to swell and dissolve [6].
Gel Strength is determined with a Bloom
gelometer [7], [8], [10–13]. A 6.67 % solution
of the gelatin sample is prepared in a special
wide-mouthed test bottle, which is then cooled
to 10.0 ± 0.1 ◦ C and kept for 17 ± 1 h for mat-
uration at this temperature. The firmness of the
resulting gel is then measured with a gelometer.
This instrument impresses a standard plunger
(12.7 mm diameter, plane surface, sharp edges)
into the surface of the gel. The force required to
depress the plunger 4 mm into the gel is the gel
strength or Bloom value of the gelatin. Commer-
cial gelatins vary from ca. 50 to 300 g Bloom.
Viscosity is usually determined by using a
calibrated viscosity pipette (Bloom pipette),
which measures the efflux time of 100 mL of
a 6.67 % solution at 60 ◦ C.
For gelatin hydrolysate, the viscosity of a
10 % or 20 % solution at 25 ◦ C is determined,
but other concentrations or temperatures are pos-
sible, according to the different uses. For mea-
surement of higher viscosity values, rotation vis-
cometers are also used.

Molecular mass fractions (≥ 200 000 D) have
some impact on viscosity, medium molecular
mass fractions (55 000 – 300 000 D) have an in-
fluence on gel strength. The viscosity of gelatin
solutions increases with increasing gelatin con-
centration and with decreasing temperature; vis-
cosity is at a minimum at the isoionic point.
Gelatin solutions should not be exposed to tem-
peratures above 60 ◦ C for prolonged periods of
time because the gel strength and viscosity de-
crease [14].
Color and clarity of gelatin and gelatin hy-
drolysate can be important for certain appli-
cations. These parameters can be measured
with a spectrophotometer, but visual assessment
against standard gelatins is also common prac-
tice. The color of gelatin depends on the raw
material and the production process. Pigskin
gelatins usually are less strongly colored than
those made from bone or hide. Turbidity may be
due to insoluble or foreign matter in the form of
emulsions or dispersions that are stabilized by
the protective-colloid action of gelatin, or can
be caused by an isoelectric haze. This haze is
at a maximum at the isoelectric point in ca. 2 %
solution [15].
Gelatin typically contains ca. 9 – 13 % mois-
ture, which can be determined by drying a sam-
ple at 105 ◦ C for 17 h.
Technical gelatins are normally specified by
their gelling power and viscosity. The test meth-
ods employed are generally similar to those used
for edible or pharmaceutical gelatins, but differ-
ent gelatin concentrations may be employed. For
lower grades of technical gelatins (and animal
glues) 12.5 % solutions (15 g in 105 mL water)
are used.
Methods for sampling and testing of animal
glues are described in an international standard
[16]. In addition to gel strength and viscosity the
measurement of moisture content, melting and
setting point, foam characteristics, pH and fat
content are also described.
In some countries the viscosity of technical
gelatin is measured with a cup viscometer, nor-
mally the Engler viscometer [17], [18], [19], and
using a 17.75 % solution at 40 ◦ C. The viscos-
ity (in degrees Engler, ◦ E) is the flow time of
the gelatin solution compared with that of an
equal volume of water at 20 ◦ C. Relationships
between viscosity measured by capillary and by
the Engler method are available [19], [20].
Gelatin 5
Gelatin also undergoes a phenomenon called
coacervation when colloidal particles separate
from the liquid phase. Coacervates are formed
when two hydrophilic sols carrying opposite
charges are mixed in suitable amounts [21]. If
gelatin from an acid-treated precursor is mixed
with gelatin from an alkali-treated precursor and
the resulting gel is prepared at pH 5 – 7, different
degrees of turbidity result. This effect depends
on the ratio of the two gelatins in the mixture and
the pH. This phenomenon arises from the forma-
tion of a complex coacervate between the gelatin
micelles with opposite charge. Adjustment of the
pH above or below the isoelectric range of both
gelatins gives a clear gel; both gelatins are now
either positively or negatively charged and hence
are mutually compatible. A common application
of complex coacervation is the use of gelatin
and gum arabic to produce oil-containing micro-
capsules for carbonless paper manufacture [22],
[23] (see → Microencapsulation, Chap. 4.1.).
By addition of plasticizers such as glycerin,
sorbitol and lubricants like stearate it is possible
to produce a blend with thermoplastic proper-
ties that can be used in extrusion and injection
molding processes [24].
2.3. Chemical Properties
Gelatin is formed by the particle hydroly-
sis of collagen protein resulting in a mix-
ture of protein fragments of varying molecular
mass (gelatin 15 000 – 400 000 Dalton, gelatin
hydrolysate < 15 000 D). The amino acid com-
position (see Table 1) corresponds to that of the
collagen from which it is derived. Hydroxypro-
line and hydroxylysine are two unusual amino
acids found in gelatin. The determination of the
hydroxyproline content can be used for identifi-
cation purposes [25].
The quantitative analysis of the elements
gives about 50.5 % carbon, 25.2 % oxygen,
17.0 % nitrogen and 6.8 % hydrogen. The ash
content of commercial gelatin varies with the
origin of the raw material and the method of
processing. Gelatins derived from pigskin con-
tain small amounts of chlorides and sulfates re-
sulting from acid treatment before extraction;
gelatin from bone and hide contains calcium and
sodium salts from the lime used in pretreatment.
6 Gelatin
Dry gelatin stored in airtight containers at
room temperature remains unchanged for long
periods. Degradation in solution may be caused
by extremes of pH, temperature and by prote-
olytic enzymes such as papain or trypsin.
Gelatin can be chemically modified to change
its properties. It undergoes typical protein re-
actions, including acylation and carbamylation
[26]. Such products include succinylated, phtha-
lated, and carbamylated gelatin. These products
are used for special pharmaceutical and photo-
graphic applications. A new type is methacry-
lated gelatin, which is suitable for technical ap-
plications. Permanent cross-linking of gelatin
can be achieved by reaction with aldehydes
such as formaldehyde, glyoxal, or glutaralde-
hyde [26].
2.4. Microbiological Analysis
Microbiological testing is in most cases carried
out according to methods described in the Eu-
ropean Pharmacopeia (Ph. Eur.) and the United
States Pharmacopeia (U.S.P.). Important test pa-
rameters are total aerobic count, including molds
and yeasts, after an incubation period of up to
5 d at incubation temperatures of 30 – 35 ◦ C and
20 – 25 ◦ C and counts of colony-forming units
on tryptic soy agar and Sabouraud agar. Tests
for Escherichia coli and Salmonella species in-
clude at least one enrichment step and detection
of typical growth on selective nutrition media.
Table 2. Gelatin specifications
Parameter Ph. Eur. limits
pH 3.8 – 7.6
Total ash, % 2 2
Loss on drying, % 15
Sulfur dioxide, mg/kg 200
Peroxides, mg/kg 100
Arsenic, mg/kg 1 0.8
Heavy metals, mg/kg 50
Phenolic preservatives 0
Total viable count CFU ∗∗ 1000/g
Escherichia coli 0 in 1 g
Salmonella 0 in 10 g
∗ Gelatin used for capsule manufacture can contain up to
1500 mg/kg. ∗∗ CFU = colony-forming units.
2.5. Quality Specifications
Gelatin, as a protein, is subject to contamination
by microorganisms; good manufacturing prac-
tice must be followed to ensure a clean product.
In addition to rendering gelatin unacceptable
for human consumption, bacteria can degrade
gelatin to a point at which it loses its gel-forming
property. Conductivity and pH have a major im-
pact on gelatin quality due to their importance
regarding optimal growth conditions for bacteria
[27].
Most gelatin manufacturing plants meet the
strict requirements of ISO 9000 [28] and ensure
consistent high quality by the implementation
of HACCP (hazard analysis and critical control
points) techniques [29]. The result is one of the
purest proteins available to the food, pharma-
ceutical, and photographic industries. As a pure,
natural protein, gelatin is a food, not an additive
and, does not carry an E number.
The majority of commercial gelatins contain
less than 3000 nonpathogenic bacteria per gram.
For pharmaceutical-grade gelatin the pharma-
copeia (Ph. Eur., U.S.P.) set a limit of 1000 bac-
teria per gram, and Salmonella species and Es-
cherichia coli must be absent in 10 g and 1 g,
respectively [9], [10]. Physical and chemical
characteristics of gelatin are listed in Table 2,
together with microbiological specifications for
pharmaceutical-grade gelatin.
Up to now there are no official limits for
microbiological, physical or chemical parame-
ters for food-grade gelatin. Therefore the Gelatin
Manufacturers of Europe (GME) cooperate with
official authorities to set microbiological, phys-
U.S. P. limits ical, and chemical limits for food-grade gelatin.
It is planned to release a monograph for food-
grade gelatin which contains not only the quality
limits but describes also the test methods to en-
40 ∗
sure compliance with those limits.
Since the raw materials are exclusively ob-
50 tained from animals fit for human consumption,
1000/g
and the production process includes numerous
0 in 10 g purification steps like washing, filtration, ion ex-
0 in 10 g change and a final UHT sterilization step, gelatin
is a safe product with regard to bacteriologi-
cal, viral, and TSE (transmissible spongiform
encephalopathies, e.g., Scrapie and BSE) safety
[30], [31] and therefore does not carry any risk
for the health of consumers.

3. Raw Materials and Production
3.1. Raw Materials
Gelatin is commercially derived from animal
collagen of skins and bones. The principle raw
materials worldwide are cattle hides, bones and
pigskins. In principle all raw materials are fit for
human consumption. Sources from other mam-
malian species and fish sometimes are also used.
Each raw material requires special treatment to
remove noncollagenous extraneous substances
such as fat and minerals. The resulting pure col-
lagen is then hydrolyzed to gelatin, which is sol-
uble in hot water.
Bones. The so-called green bones are sup-
plied by slaughterhouses and meat packers. The
fresh raw material is transported directly to the
degreasing plants of the gelatin producer. Af-
ter preselection the bones are crushed into small
particles, degreased, dried and sorted according
to size. The mineral components of bones are hy-
droxyapatite and calcium carbonate. To remove
the inorganic components the bones are treated
for about a week or more with cold diluted acid.
The resulting collagen is called ossein, the start-
ing material for subsequent gelatin extraction.
Cattle Hides. Skins from calves and beef are
obtained from animals slaughtered for human
use. The subcutaneous, fat-containing tissue is
mechanically separated and the skins are split
horizontally into two parts: the part previously
covered with hair is tanned and subsequently
used as a high-quality leather. The parts previ-
ously in contact with the flesh are the so called
hide splits. These residual thinner sections re-
main untanned and are dried or preserved with
salt or calcium hydroxide to become the raw ma-
terial used in the production of gelatin.
Pigskin. Pigskin is the most important raw
material for production of edible gelatin in Eu-
rope and United States. Pigskins are supplied by
slaughterhouses and meat processing plants and
are frequently cooled or even frozen to prevent
deterioration.
Gelatin 7
3.2. Production
Each raw material requires a special pretreat-
ment of the collagen containing material to ren-
der it soluble in hot water. During pretreatment
procedures the collagen swells and softens, pep-
tides and cross-links are hydrolyzed, and vari-
ous substances, regarded as impurities, are ex-
tracted. Two main types of gelatin are distin-
guished: type A from acid pretreated raw ma-
terial and type B from alkaline processing. The
production process is shown in Figure 2.
Acid Process. The acid process is used for
pigskin and sometimes for special types of os-
sein. Washed pigskins are treated with diluted
mineral acids for approximately 24 h at low tem-
perature. This pretreatment is sufficient to break
acid-labile peptide bonds in pigskin collagen.
After partial neutralization the gelatin is then
extracted with hot water. Usually, the gelatin is
extracted stepwise with successive increase of
temperature and time. Gelatins from successive
extractions show different physical and chemi-
cal properties. The first extract has the highest
gel strength and molecular mass and a very low
color. Later extracts, obtained at elevated tem-
peratures, contain a higher amount of low molec-
ular weight peptides and therefore have lower
gel strength and are more intensive in color and
clarity.
Alkali Process. For the production of type B
gelatin, cattle hides and ossein are pretreated
with alkali (lime or sodium hydroxide) at am-
bient temperature. The liming time varies from
several weeks to several months. The treatment
removes impurities and splits cross links and
peptides. The liming time is a critical parameter
for the further processing.
The dilute solutions obtained by hot-water
extraction contain 3 – 10 % gelatin. The liquors
are filtered and deionized to remove suspended
matter and undesirable amounts of inorganic
ions. The clarified, dilute gelatin solution is con-
centrated to 25 – 35 wt % by vacuum evapora-
tion, filtered, and sterilized. The concentrated
liquor is rapidly chilled to a gel, extruded as noo-
dles, which are deposited on a stainless steel net
for drying with hot, sterile air. The net passes
8 Gelatin

Figure 2. Gelatin production process


slowly through a drying chamber, which is di-
vided into several zones with controlled temper-
ature and humidity. Typical temperature range is
from about 30 ◦ C at the beginning up to about
70 ◦ C in the final zone. The dried gelatin, hav-
ing a moisture content of ca. 10 %, is broken
and milled. The physical, chemical and micro-
biological properties of each extract are tested.
4. Uses
4.1. General Aspects
Although basically a food stuff, gelatin has long
been valued not only for its nutritional contribu-
tion but also for its functional qualities. There-
fore, the use of gelatin is not limited to the food
industry. Very important applications are found
in the pharmaceutical, cosmetic, photographic
and technical area.
The use of gelatin in all these application
fields depends largely on the structure func-
tion relationships that influence the functionality
[33]. The main influencing molecular parame-
ters are:
– Amino acid composition and sequence
– Secondary, tertiary, quaternary conforma-
tion
– Net charge and charge distribution
– Hydrophobicity/hydrophilicity ratio
– Size and shape
– Secondary reactions (intra- and intermolec-
ular)
Hydrogen bonding
Ionic bonding
Van der Waal’s bonding
The functional role of gelatin does not arise
from a single physicochemical property, rather
it is a manifestation of a complex interaction
of multiple properties. In spite of this the ami-
no acid composition and sequence is the main
reason for several functional properties. Gelatin
is composed of about 65 % of polar or ionized
amino acids. This high proportion of these po-
lar amino acids influences hydration properties
such as solubility and water-binding capacity.
The type of hydrophobic amino acid residues
and the hydrophilicity ratio are associated with
amphiphilic behavior, which is important for
foaming and emulsifying properties.
Gelatin 9
Due to its molecular structure and its
structure – function relationship gelatin, shows
the following properties:
– Gel formation
– Water binding
– Thickening
– Emulsion formation and stabilization
– Foam formation and stabilization
– Film formation
– Adhesion / cohesion
– Protective colloid function
4.2. Food Industry
Edible gelatin and gelatin hydrolysate are widely
used ingredients in the production of food. Dif-
ferent properties and different applications re-
quire the production of suitable gelatin types
[32]. Because of the ease of measuring out the
required quantity, leaf gelatin is sold world-
wide for household use. For cream cakes and
cream desserts, special instant gelatins are avail-
able for preparing foods without heating. In the
food industry powdered gelatin and gelatin hy-
drolysate are used in the processing of confec-
tionery, dairy products, desserts, meat products,
beverages, and so on.
Confectionery. For the confectionery indus-
try, gelatin and gelatin hydrolysate are used due
to their different properties:
– In the production of gums and jellies, gelatin
is responsible for gel formation, texture, and
the bright shiny appearance.
– Aerated confectioneries such as marshmal-
lows owe their light and soft character to the
ability of gelatin to form and stabilize foams.
– In fruit chews, gelatin or gelatin hydrolysate
is used to prevent products becoming sticky.
– The film-forming properties of gelatin are
used in the production of dragees.
– In caramel and liquorice sweets, gelatin pro-
vides excellent texture and mouthfeel.
– In pastilles, an elastic structure and excellent
melting properties are provided by gelatin.
– In lozenges and compressed products, the
binding properties of gelatin guarantee re-
tention of shape.
10 Gelatin
Dairy Products. Gelatin enhances the tex-
ture of dairy products in an optimal way. Many
product properties can be controlled by using
different quantities and types of gelatin:
– Gelatin acts as a protective colloid in yogurts,
thus preventing syneresis. The consistency
can be adjusted from creamy to almost solid.
– Soft cheese can be adjusted in consistency
from creamy to sliceable.
– Cream and toppings can be stabilized to re-
tain their shapes.
– Sour cream retains its spreading and good
melting qualities.
– The ability of gelatin to bind water, form
emulsions and provide stability is exploited
in the production of low-fat dairy products.
– The melting behavior of ice cream is sub-
stantially enhanced by the improved emul-
sion and finer crystal structure made possi-
ble by the addition of gelatin. In this appli-
cation, gelatin is frequently combined with
other hydrocolloids.
Desserts. Crystal-clear, firm to soft gels are
required for dessert and fruit jellies; these can
be fulfilled by selecting the most suitable gelatin
type. In the production of whipped mousse and
cream desserts, excellent foam formation and
stability of the gelatin are important selection
criteria. Different types of instant gelatin with
different gelling properties can be used in the
production of ready-to-eat desserts, both in mass
production and in the households.
Meat and Sausage Products. Gelatin is
used as gelling agent in the production of crystal-
clear aspic meat and sausage products. Depend-
ing on the gelatin type the texture of the gel can
range from soft to sliceable. In addition gelatin
guarantees the brilliance and color of these prod-
ucts. Nongelling gelatin hydrolysates are used
in edible dips and in combination with gelatin
as adhesives in meat and sausage coatings.
Additionally both gelatin and gelatin hy-
drolysate are used to optimize the following
technological and sensory quality parameters:
– Reduction of jelly and fat residues in canned
sausage
– Improvement of spreading, quality, and soft-
ness in emulsified sandwich spreads
– Whipping agent for low-calorie sandwich
spreads
– Improved homogeneity of binding in cooked
sausage
– Protein enrichment in cured meats
– Rapid reduction of aw values (water ac-
tivity, see → Foods, 2. Food Technology,
Chap. 1.4.) and shorter maturation times in
raw sausage preparations
– Stabilization of emulsions, dispersions and
suspension
Beverages. Gelatin and gelatin hydrolysate
are used for the clarification of beverages, espe-
cially wine, fruit juices and beer. Clarification re-
moves, substances causing turbidity and/or bit-
terness and have a detrimental effect on optics
and taste. Secondly, such pre-clarification can
enhance the efficiency of subsequent centrifu-
gation. If necessary, gelatin treatment can be en-
hanced by adding silicic acid solution or ben-
tonite. This helps to give the wines and juices
the desired degree of brilliance.
Bakery Products. In the bakery industry,
powder gelatin, leaf gelatin and instant gelatin
are primarily used for the binding or gelling of
fillings, as well as for the stabilization of creams.
Other Food Applications. Other industrial
uses of gelatin in the food area are:
– Binder and gelling agent in canned seafood
and seafood aspic products.
– Protein enrichment of food such as in bever-
ages and dietetic products.
– Film former in panned confectionery prod-
ucts such as sugared almonds and hard-
panned chewing gum varieties.
– Stabilizer and film former in icings and glaz-
ings for bakery products.
– Thickener and emulsifier in soups, sauces,
and gravies.
– Emulsifier in half-fat margarines and butter.
4.3. Pharmaceuticals
Gelatin is widely used in the pharmaceutical in-
dustry: for the manufacture of soft and hard cap-
sules, as a bulking agent for the coating of water-
insoluble vitamins, as a starting material for the

production of human plasma expanders, as a pri-
mary component for surgical sponges and as a
binder in tablets. In addition to its use as an ex-
cepient (i.e., auxiliary agent in pharmaceuticals,
see above) gelatin is recommended as a food
supplement in the case of joint diseases.
The highest demand for pharmaceutical
gelatin is for the production of soft and hard
capsules. Soft capsules are made by feeding two
plasticized gelatin ribbons between two revolv-
ing dies. Pharmaceuticals – either as a liquid or
dispersed in an oil – are injected into the capsules
as they are formed. Subsequently the capsules
are dried in a two-step process.
Gelatin types used for the manufacture of
soft capsules are 150 – 175 Bloom limed bone
or limed hide, 190 – 210 Bloom acid pigskin or
acid bone or a blend of 150 – 170 Bloom acid
pigskin / limed bone and hide gelatin. Viscosi-
ties are in the range of 2.8 – 4.5 mPa · s. Acid-
processed hide and bone gelatin types are pre-
ferred for water-miscible or hygroscopic con-
tents. Due to their lower viscosity, less water can
be used for the gel mass formulation. Glycerin or
polyhydric alcohols like sorbitol are frequently
used as plasticizers. In general, the gel mass is
composed of 40 – 50 % gelatin, 20 – 30 % plas-
ticizer and water.
Hard capsules, consisting of gelatin, dyes
or pigments, and sometimes some processing
aids, are produced as two separate parts, known
as bodies and caps, by dipping stainless steel
pins into a preheated 25 – 30 % gelatin solu-
tion. Dried and prelocked hard capsules are for-
warded to pharmaceutical companies or contract
laboratories to be filled mainly with powdered or
granulated pharmaceuticals and sealed. Gelatin
types used for the manufacture of hard cap-
sules are 220 – 260 Bloom limed bone or blends
of 220 – 260 limed bone / acid pigskin gelatin
types. The use of gelatin to coat tablets is a grow-
ing market. In a process similar to the manu-
facture of hard capsules, the tablets are dipped
into a concentrated gelatin solution and dried.
In another process, the tablets are pressed into
prefabricated hard capsules and sealed. Gelatin
capsules and coatings protect pharmaceuticals
from moisture, oxygen, and microbial deterio-
ration.
Low-bloom gelatins (70 – 140 Bloom) are
frequently used to coat vitamins A, D, and E
for animal feed and human vitamin preparations.
Gelatin 11
Emulsions of oil-soluble vitamins in gelatin so-
lution containing carbohydrates are spray-dried
to give free-flowing powders. Vitamins are thus
available in a convenient and stable form that
offers protection from light and oxidation.
Specially processed gelatin types have been
successfully used as plasma extenders capable of
maintaining osmotic pressure. The osmotic pres-
sure of gelatin is strongly dependent on the av-
erage molecular weight. Thus the retention time
of the plasma extender (generally: 24 – 48 h) is
influenced by the size of the molecules. Com-
mercial products are manufactured by partial
thermal degradation of high-bloom limed bone
gelatin, followed by chemical modification with
succinic anhydride or cross-linking the result-
ing polypeptides with glutardialdehyde or isocy-
anates. Products containing ca. 3 % of degraded
and modified gelatin are liquid at room temper-
ature. Hemostatic sponges are manufactured by
whipping a sterile gelatin solution into a foam,
which is rendered insoluble by adding formal-
dehyde on drying. Gelatin sponges impregnated
with thrombin can be left in place after surgery
or extraction of teeth. Proteolytic enzymes com-
pletely digest the sponge.
Gelatin can act as a binder in the manufac-
ture of tablets. Pharmaceuticals are dispersed in
a gelatin solution and dried. The ground powder
is subsequently compressed into tablets. Glyc-
erin/gelatin masses are used for the production
of zinc / gelatin dressings and suppositories.
4.4. Cosmetics
Gelatin and more frequently its hydrolysates find
wide application in skin and hair-care products.
Hydrolyzed collagen is nontoxic and produces
no skin irritation, sensitization, or phototoxicity.
In skin-cleansing preparations, gelatin or
gelatin hydrolysates reduce the irritation poten-
tial of anionic surfactants.
Due to their affinity to hair keratin, gelatin
hydrolysates protect the structure of hair. Par-
ticularly in preparations for permanent waving,
bleaching, or coloring damage of hair structure
can be minimized.
12 Gelatin
4.5. Photography
Gelatin is an important raw material for all silver
halide based photographic materials. For this ap-
plication mostly alkaline-processed bone gelatin
types are used. As a hydrocolloid and a polyelec-
trolyte, gelatin controls growth of silver halide
crystals and prevents coagulation [34]. In ad-
dition, gelatin contains substances which influ-
ence the photographic properties of the light-
sensitive material [35]. Gelatin also stabilizes
hydrophobic additives in formulations (e.g., dye
couplers) [36], [37]. The ability to undergo re-
versible sol – gel transition combined with the
rheological properties of gelatin enable coating
of several emulsion layers at the same time on
a paper or film base [38], [39]. Gelatin can be
cross-linked by a variety of chemical substances
[40] to increase mechanical strength and stabil-
ity of the coated layers to higher temperatures
under acid or alkaline conditions without los-
ing the ability to swell. Therefore chemicals can
still diffuse through the different layers. This is
essential for the development of the latent im-
age and dye formation during processing of the
exposed photographic material.
According to their application and their use in
photographic materials, gelatin can be classified
as follows:
– Emulsion gelatin
– Oil-in-water emulsion gelatin
– Support gelatin
Emulsion Gelatin. During the precipitation
of the silver halide crystals, gelatin acts as a pro-
tective colloid. It stabilizes the silver halide crys-
tals and influences their growth and their crystal
habit. For this application highly purified lime-
treated bone gelatin is used to prevent contam-
ination of the silver halide by photographically
active substances that may otherwise be present
in gelatin. Specially modified gelatin may be
used as well. By adjusting the pH, the modi-
fied gelatin forms a coacervate. This process is
reversible and allows washing of the emulsion.
During chemical ripening, gelatin is used to
control chemical reactions of added components
with the silver halide surface in order to achieve
desired photographic properties (e.g., sensitivity
and contrast). Since gelatin itself could contain
sensitizing or restraining substances, a consis-
tent manufacturing process with a reliably high
level of purification is required.
Oil in Water Emulsion Gelatin. Gelatin is
used to aid formation of stable dispersions of or-
ganic substances (e.g., dyes and color couplers)
as finely dispersed oil droplets. For this applica-
tion the surface active properties of gelatin are
important.
Support Gelatin. The physical properties of
support gelatin are more important in these ap-
plication areas than the chemical properties.
In antihalation and antistatic coatings gelatin
serves as a binding medium for light absorb-
ing and electrically conducting materials. Other
uses are as follows:
Before a photographic emulsion is applied
to a film base, adhesion must be provided bet-
ween the hydrophobic base material and the
hydrophilic gelatin emulsion. For this purpose
so-called scrubbing gelatin, mixed with organic
solvents or acids, is applied to the substrate as
an intermediate layer [41]. Gelatin used for this
application must be free of any electrolytes that
can flocculate with the organic solvents.
Backing gelatin is applied as an additional
layer on the back side of the film base to pre-
vent curling, which is caused by the different
swelling and shrinkage behavior of the emulsion
coatings and the film base material.
Top-coat gelatin is an abrasion-resistant
layer which protects the emulsion layers against
mechanical stress, rupture, and friction. For
some applications, a glossy surface may also be
desirable.
Baryta gelatin is used as a nearly colorless
binder for a suspension of barium sulfate which
is applied to photographic papers in order to pro-
vide a highly reflective white appearance.
4.6. Technical Gelatin and Glue
Technical gelatin is a convenient term for gelatin
that is used for nonedible purposes. Chemically,
like pure gelatin, it is a mixture of proteins ob-
tained by partial hydrolysis of waste collagen
from animal connective tissue, bone, and skin.
Technical gelatins, however, usually have in-
ferior physical properties (gelling strength and

viscosity of standard aqueous solutions, mea-
sured under standard conditions) and contain a
higher proportion of nonprotein material than
pure gelatin. The nonprotein component varies
with the origin of the raw material and is usually
residual mucopolysaccharides and soluble inor-
ganic salts arising from the animal protein waste
from which the gelatins are derived.
Technical gelatin has many applications
based on its gelation and surface properties,
for example: adhesives, remoistenable adhesive
tapes, abrasives, matches, paper impregnation,
plaster manufacture, production of stabilizers
for emulsions, flocculation agents, and many
more.
4.6.1. Matches
Only very clean glues are suitable for the pro-
duction of matches, where they are applied as a
binder for the matchhead composition. The in-
clusion of very fine air bubbles in the match-
head is very important to ensure the presence
of additional oxygen and good ignition behav-
ior. Therefore the glue must show well-defined
foaming behavior as far as stability and structure
of the foam is concerned. Special test methods
and instruments have been developed to control
these important properties. As fat and grease act
as undesirable defoamers, they must be carefully
eliminated during production. Furthermore, the
glue should contain only very small amounts of
salts. Especially chlorides lower the setting point
of the glue. In countries with high humidity in the
air this leads to softening of the matchhead, ren-
dering ignition more difficult or even impossi-
ble. Cross-linking with other components of the
matchhead may counteract this undesirable per-
formance to a certain extent. Technical gelatin,
due to its high gelation power, is also used as
an adhesive to produce the slide cover of the
matchbox, which is produced at speeds of sev-
eral thousands of pieces per minute.
4.6.2. Coated Abrasives
In coated abrasives technical gelatin is used as
a binder between the paper substrate and the
abrasive component. Gelatin-impregnated pa-
pers and unglued papers are used as substrates.
Gelatin 13
Usually two coats are applied by two-roller coat-
ing devices. As a base coat a concentrated warm
gelatin solution is used to apply a thick adhe-
sive film with good spreading behavior and good
flat-lying properties. To achieve good spread-
ing properties, gelatin with certain thixotropic
properties is required. In some cases starch is
added. After the first coat the abrasive material
is added, and a high-voltage electric charge is
used to align the particles to improve the abra-
sive performance.
In addition to gelatin fillers, the second coat
may contain pigments and additives with a cross-
linking effect to toughen the dried film and to
reduce moisture sensitivity, thereby increasing
the life cycle of the coated abrasive. The coated
paper is usually dried in loops in an oven. Com-
pared with abrasive materials coated with phe-
nolic resins, gelatin provides better and more
elastic binding to the substrate. A disadvantage
is the lower water resistance. The main applica-
tion for gelatin coated abrasives is therefore the
traditional glass or sandpaper used for smooth-
ing wood, leather, and paint surfaces.
4.6.3. Paper Sizing
Technical gelatin is utilized as a size coat-
ing in the production of high-quality all-wood,
rag – wood, and rag-based papers:
– Currency and other security papers must pos-
sess high performance for multiple use, good
moisture and abrasion resistance, and good
adherence to printing inks.
– In aquarelle papers gelatin provides the de-
sired reduction in surface fluff.
– Most hand-made papers contain gelatin as
sizing agent.
4.6.4. Adhesives
Gelatin has many functions in the adhesive field.
A rough surface is required to allow mechan-
ical grab of the glue, and at least one substrate
must be permeable to water vapor to accomplish
proper bonding. Gelatin glues are generally ap-
plied as a solution at ca. 60 ◦ C. They have a
unique two-step setting behavior. If applied in
14 Gelatin

normal thickness to a substrate at room temper-
ature, gelation takes place within parts of a sec-
ond. A bond is formed which will allow handling
of the joined materials almost immediately. The
much higher final strength and the high temper-
ature resistance (up to 190 ◦ C) comes after com-
plete evaporation of the free water.
Modified gelatin glues with special additives
to develop the desired properties are used for:
– Bookcase making on fast-running machines,
where stiff cover materials with high resilient
strength must often be turned in.
– Book-spine reinforcement: Gelatin gives the
book spine the necessary stability. It is also
suitable for bonding the gauze or other ma-
terial. The glue has to form an elastic film
after drying and should have good adher-
ence to previously applied synthetic disper-
sion glues.
– Lamination of paper to cardboard: glue
based on gelatin exhibits good flat-lying
properties and long open pot life, and only
very little shrinkage of the paper is observed.
It is used for the production of posters, jig
saw puzzles and games.
– Box covering: cardboard boxes are covered
with decorative cover materials. The gelatin-
based glue must have good flat-lying prop-
erties and strong gelation power.
– Gummed tapes and papers: here often un-
modified warm gelatin solutions are used. It
is important to dry the solution with hot air to
form a glasslike film which can be activated
with cold water.
– Musical instruments and furniture: only for
high-quality products gelatin based glues are
still used today. In mass production, syn-
thetic dispersion glues have replaced tech-
nical gelatin.
4.6.5. Other Uses
– As gelatin films are nonflammable, they are
used for compostable grave lights.
– The resistance of gelatin to most organic sol-
vents opens up applications in paintbrush
production and the manufacture of paper
gaskets.
– Gelatin is used in rubber mixtures to smooth
the surface.
5. Economic Aspects
The gelatin market in total has shown only a
moderate growth of about 2 to 3 % per annum
over the last 25 years. Nevertheless, large dif-
ferences could be seen from year to year with
regard to different areas of application or geo-
graphical regions. Pharmaceutical use of gelatin
in the late 1990s increased by more than 10 %
per year in North America, South America, and
the Far East, but there was practically no growth
in Europe. The use of edible gelatin declined in
the Far East and showed no growth in Western
Europe.
Worldwide production of high-grade gelatin
in 1997 was ca. 245 000 t and ca. 50 000 t of tech-
nical gelatin (glue). The distribution of the pro-
duction is listed in Table 3.
Table 3. Gelatin production by region (in 103 t)
Territory Gelatin Technical
gelatin (glue)
Western Europe 110 8
North America 42
Asia/Australia/Africa 43 30
Latin America 42 9
East Europe 8 3
The raw material situation is summarized in
Table 4.
Table 4. Raw materials for gelatin in production

– Very fine ground gelatin is combined with Raw material Gelatin Technical gelatin
(glue)
gypsum to provide special rheological prop-
Pigskin 38 % 10 %
erties to surfacer compounds. Bones 33 % 40 %
– Gelatin is employed for partly replacing ca- Hide splits 29 % 50 %
sein in glues.
– Gelatin films exhibit antifogging behavior
and are therefore used in the production of The worldwide market shares of the different
gas masks. applications were the following:

Edible gelatin 55 %
Pharmaceutical gelatin 17 %
Photographic gelatin 11 %
Technical gelatin (glue) 17 %
Regarding production capacity the leading
manufacturers rank as follows:
High-grade gelatin
1) Deutsche Gelatine-Fabriken Stoess AG,
Germany
2) SKW Biosystems, France
3) Leiner Davis Gelatin International, Australia
4) Tessenderlo B.V., Belgium
Technical gelatin (glue)
1) Fritz Häcker GmbH & Co., Germany
2) Trobas B.V., Netherlands
3) Ind. Cola e Gelatina Campo Belo Ltda.,
Brazil
4) Colas e Gelatinas Rebière Ltda., Brazil
6. References
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3. A. Veis: The Macromolecular Chemistry of
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4. G. Stainsby: “Gelatin Gels,” in A. M. Pearson,
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5. L. Slade, H. Levine: “Polymer-Chemical
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6. R. T. Jones in K. Ridgway (ed.): Hard
Capsules Development and Technology, The
Pharmaceutical Press, London 1987,
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7. Gelatin Manufacturers Institute of America,
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8. S. Williams (ed.): Official Methods of Analysis
of the Association of Official Analytical
Chemists, 14th ed., 23, AOAC, Inc.,
Arlington, Virginia 1984, p. 429.
9. National Formulary XXIII, United States
Pharmacopeial Convention, Inc., Rockville,
Maryland 1997.
Gelatin 15
10. European Pharmacopeia, 3rd ed., European
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Manufactures of Europe, Brussels 1998.
12. O. T. Bloom, US 1 540 979, 1925.
13. British Standard 757: “Methods for sampling
and testing gelatine (physical and chemical
methods),” 1975.
14. R. Schrieber, “Edible Gelatine: Types, Uses
and Application in the Food Industry,”
Gordian 76(1976) 356 – 364.
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16. ISO 9665, Animal glues – Methods for
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17. Bulgarian Standard BDS 543-72 “Bone glue”,
1972; BDS 1560-63 “Technical gelatin”, 1963.
18. USSR Standard GOST 2067-71 “Bone glue”,
1971; GOST 3252-46 “Hide glue”, 1946.
19. C. A. Finch, S. Ramachandran: Matchmaking:
Science, Technology, and Manufacture, John
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21. J. E. Vandegaer (ed.): Microencapsulation:
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New York 1974, pp. 21 – 27.
22. National Cash Register, US 2 800 457, 1957
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23. M. H. Gutcho: Microcapsules and
Microencapsulation, Noyes Data Corporation,
Park Ridge, New Jersey 1976, pp. 3 – 60.
24. Deutsche Gelatine-Fabriken Stoess AG,
EP 0 354 345, 1993 (Deutsche
Gelatine-Fabriken Stoess AG).
25. Standardised Methods for the Testing of Edible
Gelatine, Gelatine Manufactures of Europe,
Brussels 1998.
26. R. C. Clark, A. Courts: “The Chemical
Reactivity of Gelatin,” in A. G. Ward, A.
Courts (eds.): The Science and Technology of
Gelatin, Academic Press, London,
pp. 209 – 241.
27. U. Seybold: “Mikrobiologie von Gelatine und
Gelatineprodukten,” in H. Weber (ed.):
Mikrobiologie der Lebensmittel: Fleisch und
Fleischerzeugnisse, Behr’s Verlag, Hamburg
1997.
28. International Standard Organization ISO 9000.
29. Codex Alimentarius, Food and Agricultural
Organization of the United Nations, Rome.
30. R. Schrieber, U. Seybold: “Gelatin production,
the six steps to maximum safety,” in F. Brown
(ed.): Transmissible Spongiform
16 Gelatin
Encephalopathies – Impact on Animal and
Human Health, vol. 80, Karger, Basel 1993.
31. U. Manzke, G. Schaf, R. Poethke, K.
Felgenhauer, M. Muder, “On the Nervous
Proteins from Materials Used for Gelatin
Manufacture During Processing,” Pharm. Ind.
58 (1996) 9, 837 – 841.
32. A. Schott, “Speisegelatine, Herstellung,
Eigenschaften und Einsatzgebiete,” Food.
Technologie Magazin 7(1996) 3, 14 – 20.
33. E. Dick, “Gelatine a look at functionality,” IFI
21 (1998) 2, 42 – 46.
34. M. Szücs: “Die Rolle der Gelatine während
der Fällung und des Wachstums von
Silberhalogenidkristallen,” in H.
Amman-Brass, J. Pouradier, F. Moll (eds.):
Photographic Gelatin, IAG, Fribourg 1996,
p. 338.
35. T. Ohno et al., J. Photogr. Sci. 33 (1985)
207 – 211.
Gems → Crystal Growth
General Anesthetics → Anesthetics, General
36. R. Schrieber, Gordian 73 (1973) 282 – 287.
37. http://www.dgfstoess.com
38. F. J. Moll: “Gelatin in the Photographic
Industry,” in H. Amman-Brass, J. Pouradier
(eds.): Photographic Gelatin, IAG, Fribourg
1994, p. 181.
39. T. Kobayashi et al.: “On the Rates of Gelation
and the Setting points of Gelatin Solutions,” in
M. Austin (ed.): J. Photogr. Sci. 40 (1992) p.
181.
40. T. Takahashi: “The Mechanism of the
Crosslinking Reaction of Gelatin with
Hardener,” in H. Amman-Brass, J. Pouradier,
F. Moll (eds.): Photographic Gelatin, IAG,
Fribourg 1996, p. 593.
41. W. Krafft in K. Keller (ed.): Science and
Technology of Photography, Verlag Chemie,
Weinheim 1993, p. 66.
 Genetic Engineering 1

Genetic Engineering
Nucleic Acids is a separate keyword

Tattanahalli Nagabhushan, Schering Corporation, Bloomfield, New Jersey 07003, United States
Satwant Narula, Schering Corporation, Bloomfield, New Jersey 07003, United States

1. Introduction . . . . . . . . . . . . . . 2 4.2.1. Yeast (Saccharomyces cerevisiae) . 16

2. DNA Cloning Techniques . . . . . 3 4.2.2. Other Yeast Systems . . . . . . . . . 18
2.1. Cloning Genomic DNA Fragments 4.2.3. Filamentous Fungi . . . . . . . . . . . 18
in Escherichia coli . . . . . . . . . . 3 4.3. Heterologous Gene Expression in
2.1.1. Plasmids as Cloning Vectors . . . . 4 Higher Eukaryotes . . . . . . . . . . 18
2.1.2. Bacteriophage Lambda as a Cloning 4.3.1. Mammalian Cells . . . . . . . . . . . 18
Vector . . . . . . . . . . . . . . . . . . 5 4.3.1.1. Vectors . . . . . . . . . . . . . . . . . . 19
2.1.3. Cosmids as Cloning Vectors . . . . . 8 4.3.1.2. Promoters and Enhancers . . . . . . 20
2.1.4. Bacteriophage M13 as a Cloning 4.3.1.3. Chromosomal Gene Amplification . 21
Vector . . . . . . . . . . . . . . . . . . 8 4.3.2. Insect Systems . . . . . . . . . . . . . 21
2.2. Synthesis of cDNA . . . . . . . . . . 8 4.3.3. Plant Systems . . . . . . . . . . . . . . 21
3. Methods for Screening and Identi- 4.3.3.1. Plasmid Vectors . . . . . . . . . . . . 21
fying Recombinant Clones from a 4.3.3.2. Plant Promoters . . . . . . . . . . . . 23
Library . . . . . . . . . . . . . . . . . 9 5. Applications of Recombinant
3.1. Nucleic Acid Hybridization . . . . 9 DNA Technology . . . . . . . . . . . 23
3.2. Immunodetection Techniques . . . 10 5.1. Therapeutic Agents . . . . . . . . . 23
3.3. Sequencing Techniques for DNA . 12 5.2. Vaccines . . . . . . . . . . . . . . . . . 25
4. Expression of Recombinant 5.3. Genetically Altered Organisms . . 26
Clones . . . . . . . . . . . . . . . . . . 12 5.3.1. Transgenic Animals . . . . . . . . . . 26
4.1. Heterologous Gene Expression in 5.3.2. Transgenic Plants . . . . . . . . . . . 27
Prokaryotes . . . . . . . . . . . . . . 13 5.4. Gene Therapy . . . . . . . . . . . . . 28
4.1.1. Escherichia coli . . . . . . . . . . . . 13 5.5. Diagnostics . . . . . . . . . . . . . . . 28
4.1.2. Bacillus subtilis . . . . . . . . . . . . 15 6. Regulatory and Safety Aspects . . 29
4.2. Heterologous Gene Expression in 7. Glossary of Special Terms . . . . . 30
Lower Eukaryotes (Fungi) . . . . . 16 8. References . . . . . . . . . . . . . . . 31

Abbreviations : CSF colony stimulating factor

dA deoxyadenosine
A glossary of special terms is given at
dC deoxycytidine
the end of the article (Chap. 7).
dG deoxyguanidine
A adenosine dT deoxythymidine
AIDS acquired immune deficiency syndrome DHFR dihydrofolate reductase
ADH alcohol dehydrogenase DNA deoxyribonucleic acid
ARS autonomously replicating sequence DNase deoxyribonuclease
bp base pair EGF epidermal growth factor
BKV bovine kidney virus FGF fibroblast growth factor
BPV bovine papilloma virus G guanosine
cDNA copy DNA GF growth factor
C cytidine IL interleukin
CEN centromere DNA kb kilobase
CHO Chinese hamster ovary lac lactose
cos cohesive lpp lipoprotein promoter

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 319
2 Genetic Engineering

LTR long terminal repeat biology came into existence in 1953 when Wat-
MLV murine leukemia virus son and Crick published their brilliant elucida-
mRNA messenger RNA tion of DNA structure based on X-ray crystallo-
MSV murine sarcoma virus graphic data [10]. The remaining pieces of the
ompA outer membrane protein A puzzle rapidly fell into place. Messenger ribonu-
ORI origin of replication cleic acid (mRNA), transfer RNA (tRNA) and ri-
PDGF platelet derived growth factor bosomes were characterized and their functions
PGK phosphoglycerate kinase elucidated. The mysteries of DNA replication
rDNA ribosomal DNA and DNA synthesis were revealed. Major dis-
RFLP restriction fragment length polymor- coveries leading to the rapid development of re-
phism combinant DNA technology were the establish-
RNA ribonucleic acid ment of conditions and rules governing DNA
RNase ribonuclease hybridization [11], the existence and purifica-
SV simian virus tion of DNA restriction enzymes [12], elucida-
T thymidine tion of the genetic code [13], and the discov-
Tag SV40 T antigen ery of DNA ligase [14], an important enzyme
Ti tumor-inducing that enabled in vitro joining of DNA fragments.
TNF tumor necrosis factor In 1972, DNA cloning methodology using the
t-PA tissue plasminogen activator above techniques was put into effect by Boyer,
tRNA transfer RNA Cohen, and Berg [15].
trp tryptophan The powerful potential of this technology was
UPE upstream regulatory element immediately apparent to the medical and phar-
vir virulence maceutical community, although genuine, well-
meaning concern existed over its misuse. As a
result, leading scientists and representatives of
government and industry in the United States
1. Introduction met in 1975 at Asilomar to draw up a referen-
dum governing the conduct of genetic engineer-
Genetic engineering or recombinant deoxyri- ing experiments in academia and industry. The
bonucleic acid (DNA) technology has almost be- Recombinant DNA Advisory Committee (RAC)
come a household word. The concept of genetic was formed. This committee publishes rules and
manipulation of living organisms is not new. regulations for recombinant DNA experiments
Early horticulturists, animal breeders, and mi- in the Federal Register of the United States an-
crobial geneticists practiced the science without nually.
today’s detailed knowledge at a molecular level. In the United Kingdom, guidelines are for-
The awesome precision of the new technology mulated by the Genetic Manipulation Advisory
developed by modern molecular biologists has Group (GMAG), but enforcement is under the
raised heated debates in recent years concerning jurisdiction of the Health and Safety Executive
its possible benefits and dangers. (HSE). In Switzerland the Commission of Ex-
perimental Genetics oversees recombinant DNA
Historical Aspects. Deoxyribonucleic acid, research, whereas in Japan this is the task of
the genetic material that determines heredity, the Ministry of Education. In the Federal Re-
was first isolated in 1869, by the German scien- public of Germany, the Central Commission for
tist Miescher. When DNA was later discovered Biological Safety promulgates guidelines for re-
to consist of only four basic components, it was combinant DNA research.
generally disregarded as a candidate for genetic
material because it was simple. Seventy years
after the first successful isolation of DNA, Av- 2. DNA Cloning Techniques
ery conducted his historic DNA transformation
experiments with Pneumococcus, which proved The first major step in cloning, (i.e., replicating)
that DNA and not protein carried genetic infor- a gene is to be able to isolate and manipulate a
mation [9]. The discipline of modern molecular copy of the gene. Several different routes may be

followed in cloning, depending on such factors
as the information available about the base se-
quence of the gene, the amino acid sequence of
the protein for which it codes, and the functional
activity of the protein. Some standard cloning
techniques are described in this chapter. They
are based either on cloning DNA fragments in
Escherichia coli or on synthesizing copy DNA
(cDNA). The choice of cloning system is strictly
dictated by the method of detection available.
The basic steps in gene cloning are outlined
in Figure 1. The “foreign” DNA is cut with a
specific enzyme known as a restriction endonu-
clease, in this case BamHI. The resulting frag-
ments are joined in vitro to a plasmid vector
at a unique restriction endonuclease recogni-
tion site (BamHI) by using DNA ligase. Gen-
erally, the recognition site lies within a drug-
selection marker (e.g., for tetracycline resis-
tance, Tet r ); this facilitates identification of the
clone because insertion of DNA into this site
inactivates drug resistance. The resulting re-
combinant plasmid is transformed (i.e., trans-
ferred) into bacteria (Escherichia coli), and the
recombinants are screened by plating on se-
lective drug media. In the case illustrated, the
E. coli is first plated on medium containing
ampicillin to select the ampicillin-resistant or-
ganisms. The tetracycline-sensitive, ampicillin-
resistant recombinant clones are then detected
by comparing replica plates, one containing
ampicillin and the other tetracycline. Because
the plasmid vector replicates at a high rate, large
quantities of cloned DNA can be purified from
a bacterial culture. Similar steps are involved
in cloning a gene in yeast cells. For a compre-
hensive account of cloning vectors, see [16]; for
genetic loci, see [17].
Most cloning techniques have been refined
extensively and are available as convenient kits
from several companies. For a description of
the enzymes used in genetic engineering, see
→ Enzymes, Chap. 6.
2.1. Cloning Genomic DNA Fragments
in Escherichia coli
One of the first requirements for cloning is the
availability of a vector that can carry an extra-
neous fragment of DNA in an autonomous fash-
ion. Therefore, a vector must be an independent
Genetic Engineering 3
replicon, i.e., a single, autonomously replicat-
ing genetic unit. It may be a plasmid, a bacterial
virus (bacteriophage) such as lambda or M13, or
a cosmid. Each of these vectors is easily distin-
guishable from the genomic DNA of E. coli and,
hence, easy to purify and manipulate. They all
have specific advantages, and choice of a sys-
tem usually depends on the size of the DNA
to be cloned. For short fragments, a few kilo-
bases (kb) in length, a plasmid cloning system
is generally adequate. Bacteriophages such as
lambda or M13 are excellent for cloning 10 – 15-
kb stretches of DNA. For longer DNA fragments
of 30 – 40 kb, the cosmid approach is highly rec-
ommended.
2.1.1. Plasmids as Cloning Vectors
Plasmids are circular, double-stranded, au-
tonomously replicating, extrachromosomal
DNA elements common in several species of
bacteria. For the purpose of cloning, a plasmid
must have certain features, the most important
being a small size and a relaxed mode of replica-
tion, which confer a higher copy number on the
plasmid. In the relaxed mode, plasmid replica-
tion is independent of chromosomal replication.
Consequently, the plasmid continues to replicate
even during the stationary phase following chro-
mosomal replication. In addition, one or more
selection markers are useful for both selection of
the transformants and maintenance of the plas-
mid. The selection markers are usually genes
that code for drug resistance (e.g., tetracycline
resistance, ampicillin resistance). Alternatively,
they may be auxotrophic markers; in this case,
the transformants are unable to synthesize cer-
tain substances (e.g., the amino acids leucine
or tryptophan) and cannot grow on media that
lack these compounds. The plasmid must carry
unique restriction enzyme sites, some of which
should be located within a selection marker.
An extensive list of cloning vectors is given
in [18]. One of the most widely used plasmids
is pBR322 [19] (Fig. 2) or its derivatives. De-
oxyribonucleic acid from the desired source is
cut at specific sites with an appropriate restric-
tion enzyme. More than 100 restriction endonu-
cleases are now available; they are described in
detail in → Enzymes, Chap. 6.1. In nature, these
enzymes prevent illegitimate recombination of
4 Genetic Engineering

Figure 1. Cloning of foreign DNA in Escherichia coli by using a plasmid vector and the restriction endonuclease BamHI
Amp r = ampicillin resistance gene; Tet r = tetracycline resistance gene

endogenous DNA with any extraneous foreign
DNA by degrading it. They recognize very spe-
cific base sequences in DNA, usually four to
six nucleotides long, and cut open the dou-
ble DNA strand to produce two single-stranded
overhangs, also known as sticky ends (Fig. 3).
Therefore, restriction endonucleases provide not
only a means of cutting the source DNA into
specific fragments but also a means of recogniz-
ing and inserting DNA into the vector. Insertion
into the vector can be performed within a selec-
tion marker to facilitate selection of recombinant
clones by insertional inactivation of the marker,
or it may be achieved by directional cloning. In
directional cloning the source DNA fragment is
cut with two enzymes (e.g., HindIII and BamHI)

and inserted into a vector cut with HindIII and
BamHI, for both of which it carries unique sites.
Because the HindIII and BamHI recognition se-
quences are not compatible, the vector ends do
not ligate. However, the DNA fragment that does
have both cohesive (compatible) ends is inserted
in a specific orientation within the plasmid. The
circular ligated plasmid transforms Escherichia
coli with a high frequency, and the recombinants
can be picked by means of a selection marker.
Figure 2. Escherichia coli plasmid pBR322 showing the
positions of drug resistance genes and some of the unique
restriction enzyme recognition sites
Amp r = ampicillin resistance gene; Tet r = tetracycline re-
sistance gene; ORI = origin of replication
2.1.2. Bacteriophage Lambda as a Cloning
Vector
A virus that infects a bacterial cell is known as a
bacteriophage or, simply, phage. Bacteriophage
lambda (λ) is a complex lysogenic phage of Es-
cherichia coli. It is, however, one of the most
well-characterized phages both genetically and
physiologically [20], having a typical head-and-
tail structure (Fig. 4). The λ genome is a double-
stranded linear molecule about 47 kb in length.
Each end of the DNA carries 5
overhangs that
are complementary to each other and contain
12 nucleotides. Upon injection into the E. coli
cell, these cohesive ends, appropriately termed
cos L and cos R, come together and circular-
ize the genome. Replication of the DNA occurs
via a bidirectional mode, and the head-to-tail,
tandemly arranged DNA (concatenate DNA) is
Genetic Engineering 5
packaged into the head (Fig. 4). The DNA is cut
at the cos L and cos R sites by a protein coded
by λ gene A. Assembly of the tail with the head
completes the formation of an infectious phage
particle, which is released by lysis of the host
cell. This is called the lytic cycle. Alternatively,
the phage can also undergo a lysogenic cycle in
which it is integrated into the host genome and
exists as a stable prophage.
The lytic cycle has been adopted for cloning
purposes by isolating appropriate mutants of the
λ phage. The process has now been so simplified
that the various components are supplied com-
mercially as kits by several companies such as
Invitrogen, Amersham, Pharmacia, Stratagene,
and Clonetech.
Figure 3. Recognition sequences of EcoRI, BamHI,
HindIII, and PstI
The line drawn through the double-strand sequence indi-
cates sites at which the enzyme cuts. Note that EcoRI,
BamHI, and HindIII yield 5
overhangs, whereas PstI yields
a 3
overhang.
For lytic infection, only about 60 % of the λ
genome is essential. This includes the left arm,
which carries the genes A – I for the head and
the tail proteins, and the right arm, which car-
ries the λ rightward promoter (pR) and the cos
R site. The middle portion is involved in repli-
cation and lysogeny, and is not crucial for the
lytic cycle. This feature is important because it
allows this portion to be replaced by a “foreign”
DNA fragment.
6 Genetic Engineering

Figure 4. Lytic and lysogenic life cycles of the lambda (λ) phage

To permit introduction of “foreign” DNA, the
wild-type λ phage has been modified so as to
have a single target recognition site for a restric-
tion enzyme (insertional vector) or a pair of such
sites that allow part of the phage fragment to be
replaced by the insert (replacement vector). Sev-
eral variants of such vectors were constructed by
Blattner [21], who appropriately named them
Charon phages after the mythological greek fer-
ryman.
Two of the most popular vectors of which
several derivatives are now available are λgt10

and λgt11 [22]. The λgt10 vector contains a sin-
gle EcoRI site in the CI gene [23], which codes
for the repressor of the phage lytic cycle. In-
sertion at this site inactivates the CI function.
As a result, recombinant vectors (CI− ) produce
clear plaques, whereas nonrecombinant vectors
(CI+ ) slow down the growth of the host to pro-
duce turbid plaques when grown in E. coli. Re-
combinants derived from λgt10 cloning are usu-
ally screened by using nucleic acid hybridiza-
tion (see Section 3.1). For λgt11 [24], the EcoRI
site is located within the lacZ gene which codes
for the enzyme β-galactosidase. Therefore, in-
sertion into this site inactivates the lacZ gene.
In this case, when grown in E. coli that can-
not ferment lactose (lac− ), the recombinants can
be distinguished on the basis of their ability to
form colorless plaques on X-gal plates carrying
the chromogenic substrate 5-bromo-4-chloro-3-
indolyl-β-d-galactoside (X-gal) [25]. A func-
tional lacZ gene results in the formation of dark
blue plaques due to the hydrolysis of X-gal. Re-
combinant phage particles obtained in this man-
ner are generally representative of a single ge-
netic source, such as the E. coli genome, human
genome, or hamster genome, and are called li-
braries. In the case of λgt11 libraries, the lacZ
protein is expressed. Insertion of a cDNA se-
quence (see Section 2.2) into the coding region
of the lacZ gene results in a chimeric or fusion
protein, whose proximal end represents part of
the lacZ protein. Because the “foreign” DNA is
then expressed as a protein, the λgt11 libraries
can be screened for a particular protein by means
of a specific antibody.
Almost every practicing scientist prefers to
obtain his or her λDNA in a ready-to-use pack-
age. Most companies provide the λDNA as pre-
cut left and right arms, which obviates the need
to perform this in the laboratory. Thus, genomic
DNA fragments or cDNA fragments with ap-
propriate ends can be ligated directly into the
arms. The ligated DNA is then packaged into
the phage particle. A minimum limit exists for
the length of DNA that can be packaged into the
λ head. The packaging efficiency decreases dra-
matically when the insert size is more than 105 %
or less than 78 % of the phage genome size [26].
Therefore, if the two arms were ligated directly
with each other, they would be packaged very
inefficiently.
Genetic Engineering 7
The success rate in cloning a gene is tied
intimately to the final number of recombinant
plaques screened. To obtain a complete library,
at least 106 plaques are required, which is dif-
ficult to achieve by transfection of competent
bacteria. However, use of an in vitro system for
packaging phage DNA into empty phage heads
and direct infection of the host cell yield nearly
106 recombinant plaques per microgram of lig-
ated vector DNA. The in vitro packaging system
consists of cell extracts of two kinds of heat-
induced lysogenic strains. One of these is a tail
donor strain and has a mutation in gene D, one
of the genes required for head assembly. The
other strain is a head donor strain and has a mu-
tation in a gene required for tail assembly (gene
E). Each of these is independently incapable of
forming phage particles; in the mixed extract,
however, genetic complementation occurs and
exogenous DNA is packaged in the phage heads
[18].
2.1.3. Cosmids as Cloning Vectors
Cosmids are a cross between the λ phage and a
plasmid vector; they contain the cos site (hence
the name cosmid) of a λ phage ligated into a plas-
mid vector [27]. Thus, “foreign” DNA can be in-
serted into a cosmid at a target site. Upon infec-
tion of E. coli, the cosmid circularizes but repli-
cation follows the autonomous plasmid mode
and no infectious particles are produced because
these functions are not encoded on the vector.
The resulting DNA can be packaged into phage
particles by using the in vitro packaging system
described in Section 2.1.2. Recombinant selec-
tion may be based on a drug-selection marker
encoded on the plasmid backbone.
Cosmids are extremely useful for cloning
very large eukaryotic genomic fragments. Be-
cause the size of the parent vector is several times
smaller than that of λgt10 or λgt11, for example,
a very large foreign DNA fragment may be in-
serted and packaged with efficiency in the phage
particles.
2.1.4. Bacteriophage M13 as a Cloning
Vector
Phage M13 is a single-stranded coliphage
that goes through a double-stranded replicative
8 Genetic Engineering

phase in Escherichia coli, producing about 300
copies per cell. The phage does not lyse the cell
but continuously extrudes phage particles con-
taining single-stranded DNA into the medium.
The replicating phage, however, does slow down
the growth of the infected cells, producing turbid
plaques.
Messing has adapted this phage success-
fully for genetic engineering experiments such
as DNA sequencing and site-specific mutagene-
sis [28]. Several variants have been constructed
and are available commercially. Introduction of
the lacZ gene and its promoter into a nonessen-
tial region of the phage is extremely useful. The
coding sequence of lacZ is interrupted by a
polylinker (a synthetic DNA fragment that con-
tains sites for several different restriction en-
zymes). Any one of these sites may be used
to clone either cDNA or a genomic fragment.
The ligated replicative form is then transfected
into a lac− E. coli host, and the recombinant
colonies are picked as clear plaques on X-gal
medium. The background colonies appear as
blue plaques because the lacZ function is not
interrupted. The M13 vectors are indispensable
today for the Sanger method of DNA sequenc-
ing which utilizes single-stranded templates (see
Section 3.3) and oligomer-directed site-specific
mutagenesis.
loop at its 3
end. A second polymerase reac-
tion using either reverse transcriptase or DNA
polymerase I completes the second strand syn-
thesis. The hairpin and any other single-stranded
regions are trimmed away by using the single-
strand-specific nuclease S1, which results in a
flush-ended duplex structure [30].
In a variation of this scheme, known as the
Gübler procedure, RNaseH (endoribonuclease,
E.C. 3.1.26.4) is used at the RNA · DNA hybrid
stage (Fig. 5.) This nuclease creates nicks in a
RNA · DNA molecule. These nicks are extended
and filled in by using Escherichia coli DNA po-
lymerase I, which has both a 3
→ 5
exonuclease
activity and a 5
→ 3
polymerase activity. In the
final step, T4 DNA polymerase is used to elim-
inate any persisting 3
overhangs. This method
gives a superior yield compared to the original
method [31].

2.2. Synthesis of cDNA

The synthesis of cDNA is used for cloning when
the primary aim is to obtain the protein product
of the gene.

Preparation of cDNA. The enzyme reverse

transcriptase (E.C. 2.7.7.49) is a kind of DNA
polymerase found only in retroviruses (see
→ Enzymes, Chap. 6.2.4.) [29]. It differs from
other DNA polymerases by synthesizing DNA
from an RNA, and not a DNA, template. Be- Figure 5. Scheme for cDNA synthesis according to the
cause most eukaryotic mRNA molecules con- Gübler procedure
tain a 3
-hydroxyl polyadenosine (polyA) tail, See text for explanation.
an oligodeoxythymidine (dT) primer is used to
prime the reaction. The resultant structure is
a DNA · RNA hybrid. The RNA strand can be Insertion of cDNA into the Vector.
destroyed with alkali, leaving a single-stranded Double-stranded cDNA may be inserted into the
cDNA copy of the original mRNA. The single- vector of choice. For insertion into plasmids,
strand cDNA is apparently capable of self- cosmid, or M13 vectors, synthetic oligomeric
priming due to formation of a transient hairpin DNA fragments (linkers) that carry the recog-

nition site for a desired restriction enzyme are
ligated to the ends of the cDNA. The resulting
fragment is then cleaved and ligated into the
vector cut with the specified restriction endonu-
clease.
For insertion into plasmid vectors, a ho-
mopolymer tailing reaction is used which em-
ploys the enzyme terminal deoxyribonucleotidyl
transferase (E.C. 2.7.7.31) [32]. This enzyme
catalyzes the addition of deoxynucleotides to
the 3
hydroxyl terminus of a DNA primer. In
most cases, the plasmid pBR322 is cut at the PstI
site and tailed with oligodeoxyguanidine (dG),
and the cDNA is tailed with oligodeoxycytidine
(dC). When the cDNA is annealed to the linear
plasmid backbone, the PstI site is regenerated,
providing a convenient means of excising the
inserted DNA by using PstI [33]. Alternatively,
dA – dT tailing may be used. Because dA – dT
polymers have a lower melting point than dC –
dG polymers, the inserted DNA may be excised
with S1 nuclease under partially denaturing con-
ditions [34].
The Okayama and Berg cloning system, first
described in 1982 [35], is becoming increas-
ingly popular because it yields full-length or al-
most full-length cDNA clones with a very high
efficiency. The main feature of this strategy is
that the entire cDNA synthesis is carried out on
the plasmid. The process is initiated by using a
plasmid primer tailed with oligo(dT) to which
the polyadenylated mRNA is annealed (Fig. 5).
The cDNA is tailed with oligo(dC) and annealed
to an oligo(dG)-tailed, plasmid-derived linker.
All subsequent steps are essentially as described
above. This procedure has also been adapted to a
mammalian cloning vector pCD [36]. The mam-
malian system provides an added advantage in
that the cloned cDNAs can be screened directly
for expression, because the vector carries all the
essential regulatory sequences such as promot-
ers, splice signals, and polyA signals.
3. Methods for Screening and
Identifying Recombinant Clones
from a Library
3.1. Nucleic Acid Hybridization
Double-stranded DNA can be melted at high
temperature (>90 ◦ C) to yield two single
Genetic Engineering 9
strands, a process termed denaturation. Under
suitable conditions these single strands reasso-
ciate to give the original double-stranded struc-
ture; this is termed renaturation. Renaturation
can take place between any single-stranded nu-
cleic acids as long as their nucleotide sequences
are complementary, i.e., DNA – DNA, RNA –
DNA, or RNA – RNA. This provides a sensitive
method for detecting recombinant clones. Sev-
eral quick and convenient hybridization methods
have been devised for library screenings and de-
tecting specific DNA or RNA sequences.
Plaque-Lift Hybridization. When screen-
ing phage libraries, the phage plaques obtained
in agar plates can be lifted onto a nitrocellulose
filter by simply placing the filter on the agar sur-
face [37]. The filters are then treated to lyse the
phage particles, and the released DNA is de-
natured and fixed. The filters can then be hy-
bridized by using a radioactively labeled DNA
or RNA probe under appropriate hybridization
conditions. The positive plaques can be identi-
fied by autoradiography (Fig. 6). A plaque that
gives a positive signal in the primary screen
(Fig. 6 A) is isolated, and the putative recom-
binant phage derived from this plaque is used
to infect a fresh Escherichia coli culture. The
plaques are once again analyzed as described
previously; in this second step, a severalfold in-
crease in plaque purification occurs (Fig. 6 B).
The process is repeated a third time with a single
isolated plaque; in the third step, total purifica-
tion is usually achieved (Fig. 6 C).
Colony Hybridization. In a process similar
to plaque-lift hybridization, nitrocellulose repli-
cas of crowded bacterial colonies may be made
[38]. The filters are then treated with detergents
such as sodium dodecyl sulfate to lyse the cells
and release the cellular contents. The filters are
baked to fix the nucleic acids, at which point they
are ready for hybridization with the radioactively
labeled probe. The positive colonies are evident
on autoradiography and can be picked from the
original master plate for further investigation.
Southern Blotting. Southern blots provide a
means of localizing specific DNA fragments
within a mixture [39]. The fragments are first
10 Genetic Engineering
Figure 6. Three-step purification of a recombinant plaque by using plaque-lift hybridization and autoradiography for identi-
fication
Positive plaques are blackened (arrow) and their proportion increases in successive purification stages (A, B, and C). In the
final step (C), all plaques give a positive signal, indicating a pure clonal preparation.
separated by gel electrophoresis. After denatu-
ration, the DNA is transferred by passive diffu-
sion to a nitrocellulose filter by placing the gel
on the nitrocellulose sheet and then immobilized
by baking the filter for 2 h at 65 – 80 ◦ C in a vac-
uum oven. A radioactive DNA or RNA probe
can be used to locate the band of interest. The
technique is applied mainly to confirm the pres-
ence of a specific sequence in cloned DNA. It is
also extremely useful for locating sequences in
total eukaryotic DNA (Fig. 7).
Northern Blotting. Northern blots are usu-
ally applied after confirming the identity of a
clone. The RNA, not DNA, isolated from the
appropriate cell sources is electrophoresed and
transferred to a nitrocellulose filter as described
for Southern blotting [40]. Hybridization with
the cloned DNA probe can yield useful infor-
mation such as confirming the transcription of
the cloned piece of DNA as well as the number
of copies of RNA that are synthesized. This pro-
cedure may also be used to test various tissue
sources for the presence of a particular RNA.
By using appropriate probes, the start and stop
sites of transcription and regions that are spliced
out of RNA during RNA processing can also be
identified [41].
Preparation of Radioactively Labeled
Probes. Probes for nucleic acid hybridization
are labeled primarily with radioactively tagged
nucleotides. A double- or single-stranded DNA
or RNA fragment may be labeled at the 5
end by
using a γ 32 P-labeled ribonucleotide. Probes of
very high sepecific activity can be prepared by
using a technique called nick translation [42].
Here, nicks are produced in a double-stranded
DNA fragment with DNase I and subsequently
filled in with radioactively labeled nucleotide
triphosphates by using DNA polymerase.
3.2. Immunodetection Techniques
Detection techniques based on immunochemi-
cal methods are extremely useful in screening
expression libraries such as λgt11. The recom-
binant plaques are lifted onto nitrocellulose as
described in Section 3.1. A specific antibody
is used in the first step to bind to the recom-
binant protein. In the second step, this anti-
body reacts with a species-specific antibody that
is either radioactively labeled or tagged with
an indicator enzyme (e.g., alkaline phosphatase
or horseradish peroxidase). In the former case,
autoradiography is used to detect the positive
clones; with the latter, the substrate gives a chro-
mogenic response on reaction with the enzyme.
A variation of this technique is popularly re-
ferred to as Western blotting [43]. Cellular ex-
tracts or mixtures of proteins are electrophoresed
on a polyacrylamide gel and transferred by elec-
troblotting techniques to a nitrocellulose sheet.
Detection techniques are identical to those de-
scribed for plaque-lift assays. The Western tech-

nique is extremely useful for identifying a spe-
cific protein in a mixture of proteins and also
yields information on approximate protein size.
It is used widely as an identification test in the
course of expressing a protein.
Figure 7. Southern blotting
The amplification of human interleukin-4 (IL-4) is followed
on increasing concentrations of methotrexate (see Section
4.3.1.3) by using a “nick-translated” radioactively labeled
probe (see below)
a) Lambda DNA HindIII marker; b) Mouse fibroblast cell
line (L cells) transfected with Hu IL-4 cDNA plasmid;
c) “Unamplified” Chinese hamster ovary (CHO) cell line
transfected with Hu IL-4 cDNA plasmid; d) – f) Sister clones
of CHO cell line transfected with Hu IL-4 cDNA plasmid
and selected on 500 nmol/L methotrexate for DNA amplifi-
cation (see Section 4.3.1.3.). Arrow points to the band cor-
responding to the 1L-4 coding sequence.
3.3. Sequencing Techniques for DNA
The development of rapid DNA sequencing
techniques has facilitated characterization of a
cloned sequence. The DNA sequence reveals im-
portant features such as the location of the re-
striction sites and open reading frames which
may be used to deduce the amino acid se-
Genetic Engineering 11
quence of the protein. Sequencing of DNA is
carried out either by the method of Maxam
and Gilbert [44] or by the dideoxy method
described by Sanger [45]. Several automated
DNA sequencers are now available. Most of
these use Sanger’s dideoxy method of sequenc-
ing. An innovative approach employs fluores-
cent dyes to label the nucleotides, thus allowing
direct readout of the gels [46].
Figure 8. Autoradiogram of a DNA sequencing gel run ac-
cording to Sanger’s dideoxy method
The gel is “read” as described in the text (Section 3.3). Part
of the base sequence is shown.
The Maxam and Gilbert method is based on
the random cleavage of a DNA fragment by
chemicals that cleave specifically at A, G, C,
or T residues. Each of these reactions is car-
ried out separately, and the four mixtures are
electrophoresed on adjacent lanes of a polyacry-
lamide gel. The resulting fragments are sepa-
rated strictly on the basis of their size. Because
the starting DNA fragment is radioactively la-
12 Genetic Engineering
beled at the 5
end, the fragments on the gel can
be detected by autoradiography. The sequence is
read by starting with the lowest band and mov-
ing upward in a serial fashion, identifying bases
by the lanes into which they fall.
The Sanger method uses a chain-terminating
dideoxynucleotide. Here, the reaction depends
on enzymatic synthesis of a complementary
copy of a single-stranded DNA template (hence,
the importance of cloning into single-stranded
phage vectors such as M13; see Section 2.1.4).
The substrate contains a mixture of the four nu-
cleotide triphosphates, one of which is radioac-
tively labeled. The reaction is performed on four
mixtures, each of which contains one of the
four specific dideoxy nucleotides at concentra-
tions calculated to yield random terminations.
Reaction is initiated by addition of the Klenow
fragment of DNA polymerase (see → Enzymes,
Chap. 6.2.2.). The reaction mixtures are elec-
trophoresed in parallel lanes, and the gel is read
as described for the Maxam and Gilbert method
(Fig. 8).
4. Expression of Recombinant
Clones
The production of proteins from recombinant
DNA (i.e., expression) is an important as-
pect of genetic engineering. Escherichia coli
has been extremely useful in the expression
of foreign proteins that do not require post-
translational modification for activity [47], [48].
However, in the case of complex proteins, (e.g.,
blood factor VIII), or proteins requiring post-
translational modification (e.g., glycosylation
or phosphorylation) for bioactivity, alternatives
must be sought because E. coli is not capable
of carrying out this task. Other major problems
associated with E. coli are instability of the for-
eign mRNA or protein. Also, although expres-
sion levels as high as 40 % of the total cellu-
lar protein are achievable, the “foreign” protein
often forms large, insoluble aggregates called
inclusion bodies. This presents the problem of
denaturing and refolding the foreign protein in
vitro. Therefore, research on gene expression in
lower eukaryotes (e.g., yeast) and in mammalian
cells has gained prominence. The expression of
foreign genes in a heterologous organism (i.e.,
from a different species) has drawn attention to
the intermediate stages in expression of a pro-
tein, each of which may be rate limiting in the
case of a foreign protein. Because the expression
of high levels of a foreign protein is not essen-
tial to the functions of the host organism and may
even be deleterious to its survival, a major area
of research has been directed toward optimiza-
tion of regulatory parameters for transcription,
translation, and protein turnover.
Another aspect of heterologous gene expres-
sion concerns large-scale culture of the host or-
ganisms such as E. coli, Bacillus subtilis, fungi,
and mammalian cell lines. Because the phar-
maceutical industry already had extensive ex-
perience in large-scale fermentation of several
antibiotic-producing bacteria, E. coli fermen-
tations were standardized very quickly. Sim-
ilarly, the brewery industry’s experience with
yeast was useful in dealing with recombinant
yeasts. The greatest challenge was the scaleup
of mammalian and plant cell lines. Many spe-
cialty houses mushroomed quickly to deal with
this problem, which resulted in several inge-
nious technical innovations in this area. These
include growth of cells on a synthetic micro-
carrier surface, gel entrapment of cells, and the
growth of cells on solid matrices such as hol-
low fibers, collagen, or glass (→ Immobilized
Biocatalysts) [49]. Most modern biotechnology
companies can deal with large-scale growth of
recombinant mammalian cell lines. For further
details of biotechnological considerations, see
→ Biotechnology.
4.1. Heterologous Gene Expression in
Prokaryotes
4.1.1. Escherichia coli
Escherichia coli is, by far, the most widely ex-
ploited prokaryote host for gene expression. The
primary reason for this is that for decades E. coli
has been the “workhorse” of microbial geneti-
cists and, hence, its genetics and physiology are
well-known. Early vector systems were based
on the lambda bacteriophage and ColEI, an in-
digenous E. coli plasmid carrying the gene for
the antibiotic colicin. Some of the earliest gene
fragments to be cloned were well-studied E. coli
promoters such as lac (lactose) [50], trp (tryp-
tophan) [51], and λ PL [52].

Plasmid Vectors. Both inducible and consti-
tutive plasmids with high copy numbers have
been developed [53]. Constitutive high-copy
plasmids arise from mutations in the control
elements that regulate plasmid replication. In-
ducible high-copy mutants also have mutations
in these elements but maintain a low copy num-
ber until they are induced. Inducible systems
are generally preferred because the lower copy
number of the uninduced plasmid allows more
rapid cell growth. Both thermally and chemi-
cally inducible plasmid vectors have been used
successfully in Escherichia coli [54]. On induc-
tion, these plasmids lose control over their repli-
cation and are termed runaway replication, high
copy number mutants. The induced high copy
number results in a dosage increase of the re-
combinant gene, generally with a concomitant
increase in expression levels. However, the in-
crease in expression level depends on the nature
of the protein being expressed and may not be
directly proportional to the copy number [55].
Most runaway-replication plasmids reach a copy
number of 2000 per cell. Such intensive replica-
tive activity tends to exhaust the cell’s synthetic
machinery and may even lead to plasmid insta-
bility. Also, in the case of inducible promoters
such as lacUV5 and λ PL , it can very quickly di-
lute the repressor, making the system uncontrol-
lable. Overexpression of certain genes such as
tetracycline resistance can lead to plasmid insta-
bility. Plasmid stabilization technology has been
developed and assures that plasmid loss is mini-
mized to 10−4 – 10−6 cells per generation [56].
A plasmid stabilization system based on valine
synthetase has also been developed [57]. Here,
an E. coli host without valine synthetase activity
is used, and its viability is assured by the pres-
ence of valine synthetase on the plasmid. This
may be especially important when expression
of a protein that is toxic to E. coli is desired be-
cause cells which have lost the plasmid possess a
distinct advantage over plasmid-containing cells
and could rapidly overgrow the culture.
Promoter Systems. A promoter is a con-
served regulatory genetic sequence that is rec-
ognized by RNA polymerase for the initiation
of mRNA transcription. The expression level of
a heterologous protein must be directed by a
host-specific promoter to achieve a high level of
expression. One of the major efforts in genetic
Genetic Engineering 13
engineering has been to identify and construct
strong promoters that have a high rate of tran-
scriptional initiation.
A number of strong, inducible promoters
have been developed based on the knowledge
of endogenous Escherichia coli promoters such
as trp, lac, lpp (lipoprotein promoter), and λ PL .
In addition to natural promoters, several genet-
ically engineered promoters have also been de-
veloped. An example is the tac promoter, which
is a hybrid composed of the “−35 region” of
the trp promoter and the “−10 region” of the
lacUV5 promoter. It is stronger than either of the
promoters from which it was constructed [58].
An extremely elegant, well-controlled expres-
sion system has also been developed in which
the promoter and the gene to be expressed are
maintained on separate plasmids [59]. Thermal
induction of specific λ bacteriophage functions,
that are maintained on the host chromosome re-
sults in specific recombination between the two
plasmid species and expression of the recom-
binant gene. Bacteriophage T7 has also been
exploited in several gene expression systems
which rely on the fact that T7 RNA polymerase
recognizes only T7 promoters and that E. coli
RNA polymerase cannot recognize T7 promot-
ers. Therefore, a gene cloned under the control of
a T7 promoter is expressed only in the presence
of T7 RNA polymerase. By placing the expres-
sion of T7 RNA polymerase under the control
of an inducible E. coli promoter, the system can
be turned on for heterologous gene expression.
One such system relies on the presence of the T7
RNA polymerase gene which has been placed on
the host cell chromosome [60].
Translational Efficiency. The efficiency
with which a heterologous protein is translated
from mRNA in Escherichia coli may be affected
by parameters such as the ribosome binding site,
the nucleotide sequences surrounding the ribo-
some binding site and the initiation codon [61],
as well as codon usage within the gene [62].
In some cases, the secondary structure of the
heterologous mRNA impedes efficient transla-
tion [63]. Addition of DNA sequences coding
for several amino acids 3
of the start codon
increases the expression level of bovine growth
hormone from less than 0.5 % to ca. 30 % of
the total cell protein, with either a trp or an lpp
promoter [64]. This effect is probably mediated
14 Genetic Engineering
by an alteration in mRNA secondary structure
that results in enhanced amenability to trans-
lation. Computer-assisted molecular modeling
can be used to predict the secondary structure
and introduce modifications that will yield better
translation.
Secretory Systems. Escherichia coli secre-
tory systems sequester the recombinant protein
within the periplasmic space. The pINIII ompA
system relies on the lpp – lac hybrid promoter
along with the ompA signal peptide [65]. An-
other system is based on the E. coli alkaline
phosphatase promoter and signal sequence [66].
The ompA signal peptide is derived from the
gene encoding ompA (outer membrane protein
A) in E. coli. The signal peptide is responsible
for translocating the protein to the outer mem-
brane. Both of these systems are inducible and
have the following advantages:
1) Proteins are removed from the cytoplasm,
thereby reducing toxic effects on the cell.
2) Exposure of the recombinant protein to cy-
toplasmic proteases is reduced, thus facili-
tating purification.
3) Proteins are obtained with their natural ami-
no termini.
Escherichia coli does not usually secrete
proteins into the medium. Attempts using
hemolysin [67] and staphylococcal protein A
amino terminal sequences [68], however, show
promise and are being pursued in several labo-
ratories.
Proteolytic Degradation and Fusion Pro-
teins. One of the problems encountered dur-
ing the expression of heterologous genes in Es-
cherichia coli is the proteolysis of the foreign
protein. With small proteins, this problem may
be overcome by using a lon− or htpR− host
background. The gene lon encodes the primary
proteolytic activity, protease La, expressed dur-
ing heat shock [69]; the lon− mutation inacti-
vates this protease. The htpR− mutation results
in inactivation of the repressor regulating the ex-
pression of the heat-shock operon. This operon
codes for several proteases, including protease
La. Because expression of a “foreign” protein
can also trigger the heat-shock response, lon may
play a major role in protein degradation. The
htpR locus encodes a positive regulator of heat
shock [70]. Therefore, an htpR mutation leads to
nonexpression of heat-shock genes. The additive
effect of lon and htpR suggests that other pro-
teolytic enzymes may exist besides the protease
La encoded by the lon gene.
The rate of proteolysis can also frequently be
reduced if the recombinant protein is expressed
as a fusion protein. This may be accomplished
by using either an assembly of several copies of
the gene of interest arranged one behind the other
(tandem copies) [71] or an additional peptide se-
quence that can be cleaved after purification of
the protein, e.g., collagen sequences [72]. Alka-
line phosphatase fusion proteins have also been
used to identify secretory mutants that show an
increased level of expression of human growth
hormone [73].
4.1.2. Bacillus subtilis
Bacillus subtilis, a gram-positive sporulating
microorganism, has been explored extensively
for the expression of foreign proteins. One of its
most attractive features is the potential for secre-
tion of foreign proteins into the culture medium.
The surface of these organisms is enclosed by a
simple, single cell-membrane system; they can
thus secrete very high levels of some intrinsic en-
zymes. For example, up to 10 g/L of α-amylase
(10 – 20 % of the total cellular protein) can be
secreted by some industrial strains. Most of the
proteins secreted into the growth medium by B.
subtilis contain a signal peptide at the amino ter-
minus. Translocation of the protein is guided by
the signal peptide. The signal peptide is cleaved
prior to release of the mature protein into the
culture medium.
Another major advantage of B. subtilis is that
it does not secrete any endotoxins. Furthermore,
the fermentation industry has experience with
this organism.
Plasmid Vectors. Bacillus subtilis itself has
very few endogenous, naturally occurring plas-
mids; hence, most vectors have been de-
rived from other gram-positive bacteria, mainly
Staphylococcus aureus. These multicopy vec-
tors replicate autonomously in Bacillus in a rel-
atively stable manner. The most common vec-
tors and plasmid progenitors available today are
pUB110 [74], pC194 [75], and pE194 [76]; they
 Genetic Engineering 15

are all derived from S. aureus. The most im- in many cases, expedited industrial use of re-
portant selection markers used are resistance combinant strains.
genes to chloramphenicol, erythromycin, and
kanamycin. Several bifunctional plasmids that
are capable of replication in both E. coli and B.
subtilis (e.g., pVH33 [77] and pBS42 [78]) are
also available.

Promoter Systems. The α-amylase pro-

moter –signal sequence is the most widely used
regulatory sequence in Bacillus subtilis. Proteins
such as staphylococcal protein A [79], human
α-2-interferon [80], human γ-interferon, and
Escherichia coli β-lactamase [81] have been
expressed by using this system. Levels of se-
creted proteins range from 1 mg/L to 2 g/L. One
of the major problems encountered, at least in
the expression of human α-interferon, is seques-
tration of the precursor molecule as insoluble
aggregates in the cytoplasm. Secretion of het-
erologous proteins hooked up with α-amylase
signal is not always as efficient as that of the
natural protein and is very dependent on the
nature of the “foreign” protein. In addition to
α-amylase, signal sequences from B. amyloliq-
uefaciens alkaline protease and serine proteases
[82] and B. licheniformis penicillinase [83] have
also been used for the expression of heterolo- Figure 9. Photomicrographs of fungi used in genetic engi-
gous proteins. neering
A) A commonly used laboratory strain of the unicellular
yeast Saccharomyces cerevisiae. Notice the various stages
Extracellular Proteases. Bacillus subtilis of “budding” which indicate cell division; B) Aspergillus
secretes large quantities of extracellular pro- nidulans, a filamentous fungus currently being investigated
teases, especially during the onset of sporula- as a host for production of heterologous proteins
tion. This has been a major hurdle to expressing
large quantities of heterologous proteins. To
overcome this problem, attention has turned to 4.2.1. Yeast (Saccharomyces cerevisiae)
obtaining host mutations that eliminate these
proteases. Some mutants are now available, and Heterologous gene expression systems in yeast
their use has improved secretion levels of some were pursued partly for the same reasons as the
heterologous proteins [82], [83]. Escherichia coli systems. The genetics of the
yeast Saccharomyces cerevisiae, chosen for this
purpose, have been well studied. Yeast also of-
4.2. Heterologous Gene Expression in fers the facility of a secreted product. The most
Lower Eukaryotes (Fungi) appealing feature of the yeast system, however,
is that it is eukaryotic; thus, yeast cells can splice
Fungi are a valuable source of commercially im- mRNA precursors and carry out the posttransla-
portant natural products such as enzymes, vi- tional modifications (e.g., glycosylation, acety-
tamins, and amino acids. They are also widely lation, proper folding) that are essential if a eu-
used for fermentation processes. Both yeast and karyotic protein is to be fully functional.
filamentous fungi (Fig. 9) have been exploited Although a number of recombinant prod-
widely for these purposes. The vast experience ucts have been expressed in yeast at high lev-
of industry in the growth of these organisms has, els [84], expression levels are usually low com-
16 Genetic Engineering
pared to those in E. coli or mammalian cells
[85]. Another problem is the unfaithful cleav-
age of the heterologous product [86], which in-
evitably leads to severe problems in downstream
protein purification. Although yeast was initially
thought to be the ideal host, several promising
features have fallen short of expectations; e.g.,
splicing functions are limited and do not follow
the course generally observed in mammalian
cells [87]. A major problem, especially in Sac-
charomyces, is hyperglycosylation of the het-
erologous product. Also, in certain cases, Sac-
charomyces has failed to glycosylate a given pro-
tein at its known glycosylation sites [86]. Yeast
does not conform to mammalian systems in the
manner in which it glycosylates a given protein
[88]. Furthermore, the codon usage of yeast is
very different from that of either E. coli or mam-
malian systems [89].
Plasmid Vectors. Two types of plasmid have
been used widely for the expression of heterol-
ogous proteins in yeast: the 2-micron (2 µ) and
the ARS plasmids.
2 µ Plasmid. The 2 µ plasmid is derived from
an endogenous yeast plasmid that exists in the
cell at a high copy number ranging from 50 to
100 [90]. By combining this plasmid with Es-
cherichia coli plasmid pBR 322, several shuttle
vectors have been constructed. These plasmids
can replicate autonomously in both E. coli and
yeast. They are extremely useful because they
facilitate use of E. coli for all preliminary ge-
netic manipulation, in addition to the ease of
obtaining DNA from E. coli. The major disad-
vantage of using autonomously replicating plas-
mids is their inherent instability. This problem
can be partly overcome by using 0− strains of
yeast which lack endogenous 2 µ plasmids. Such
plasmids have been used successfully to produce
large quantities of desired proteins.
ARS Plasmid. The ARS plasmids contain an
Autonomously Replicating Sequence which was
originally isolated from the yeast genome and
confers autonomous replication function on
plasmids in this organism [90]. Several ARS se-
quences have been isolated (e.g., ARS1 [91],
ARS2 [92], and ARS3 [93]). Sequence analy-
sis indicates limited homology between the ele-
ments.
Like the 2 µ plasmids, the inherent problem
with ARS plasmids is their relatively low stabil-
ity, especially during mitotic growth [94]. This is
generally attributed to competition for the initi-
ation factors for DNA replication and their pref-
erential segregation into the parent cell [95]. The
ARS plasmids can be stabilized by introduction
of centromeric DNA (CEN) [96] and become
true minichromosomes. Mendelian segregation
of the circular minichromosome then occurs dur-
ing meiosis and confers plasmid stability in mi-
totic segregation. Several CEN elements have
been identified and display significant homology
[97]. The stability of CEN plasmids approaches,
but does not equal, that of normal chromosomes.
Integrating Plasmids. Yeast can be trans-
formed with linear plasmid DNA that is cleaved
within a region showing homology with the
DNA of the yeast genome. Plasmid integration
is then targeted to the homologous genomic se-
quence [98]. Furthermore, multiple copies of
the plasmid are found integrated into the yeast
genome in a tandem array [99]. By using the
URA3 gene, this approach has been employed
successfully to express high levels of heterolo-
gous proteins [100].
Linear Plasmids. Linear plasmids that are
capable of autonomous replication in yeast are
also called artificial chromosomes. They were
initially constructed by flanking linear plas-
mids with terminal sequences of extrachromo-
somal ribosomal DNA (rDNA) from Tetrahy-
mena [101]. Large linear plasmids that can exist
in one or two copies per cell were found to be
more stable than short linear plasmids or circu-
lar ARS and CEN plasmids. Their behavior dur-
ing meiosis follows a strict Mendelian pattern of
segregation.
Promoter Systems. A number of endoge-
nous yeast promoters have been developed for
the expression of heterologous proteins. The
phosphoglycerate kinase (PGK) promoter and
the 5
coding region for PGK have been fused to
the 5
end of the human α-interferon gene. This
inducible system has resulted in the expression
of a PGK –α-interferon fusion protein as 1 – 2 %
of the total cellular protein [84]. The PGK pro-
moter has also been used to express human
γ-interferon [86]. Another inducible promoter,
derived from the acid phosphatase gene, has

been used in the expression of hepatitis B sur-
face antigen [102]. The promoter derived from
the yeast alcohol dehydrogenase gene (ADH1)
has been used to express human α D-interferon
[85]. Other useful promoters are the GAL1 pro-
moter, which is positively regulated by galactose
[103], the extremely strong glyceraldehyde-3-
phosphate dehydrogenase promoter [104], and
the α-factor promoter [105].
Secretory Systems. A number of yeast se-
cretory systems have been developed. One such
system relies on the signal sequence derived
from the yeast mating factor, mat-α, and has
been used to express human epidermal growth
factor [105]. Interestingly, this gene could not
be expressed intracellularly. When fused to the
α-factor signal sequence, the protein is se-
creted and correctly folded. The system, us-
ing a 2 µ-based plasmid, has been shown to
process and secrete several proteins such as
murine granulocyte – macrophage colony stim-
ulating factor (GM-CSF) [106] and human
interleukin-2 (IL-2) [107]. However, this system
does not work with every protein. Smaller pro-
teins such as growth factors seem to be more
amenable to secretion than larger molecules.
Other secretion signals such as SUC2 and Pho5
have also been employed to secrete heterologous
proteins into the culture medium [88].
In most of the secretory systems, although
a major proportion of the protein is directed
into the secretory pathway, only a small frac-
tion is secreted into the medium [85], [86], [88].
Obviously, rate-limiting steps exist. One way
to overcome this problem is to isolate mutants
with elevated levels of secretion–supersecreting
mutants–which has been accomplished for chy-
motrypsin [88]. An encouraging aspect of the
study is that these “supersecretory” mutants can
be used with other expression – secretion sys-
tems, as well as for expressing heterologous pro-
teins other than chymotrypsin [88].
4.2.2. Other Yeast Systems
The methanol utilization pathway of Pichia pas-
toris consists of genes that are responsive to
methanol. The product of one of the genes, al-
cohol oxidase, makes up as much as 30 % of the
cell’s soluble protein. The regulatory sequence
Genetic Engineering 17
of this gene has been isolated and used for ex-
pression of heterologous proteins at high levels
[108]. Expression can be controlled by switch-
ing carbon sources from glucose to methanol.
Another appealing feature of Pichia is that, un-
like Saccharomyces, it does not hyperglycosy-
late the proteins [108].
4.2.3. Filamentous Fungi
The direct appeal of filamentous fungi as hosts
for heterologous gene expression derives from
the fact that they secrete vast amounts of en-
zymes. Under optimal fermentation conditions,
Aspergillus niger secretes up to 20 g/L of the
enzyme glucoamylase from a single copy of
the gene! By using the framework provided
by yeast, the technology for gene expression
in filamentous fungi is undergoing rapid devel-
opment. Both A. nidulans (Fig. 9 B) and Neu-
rospora crassa are eligible candidates because
they are the most widely studied filamentous
fungi.
Plasmid Systems. Attempts to isolate en-
dogenous natural plasmids from Aspergillus
and Neurospora have not been successful. The
plasmid pDJB3 was the prototype for subse-
quent work [109]. It contains the ampicillin
resistance gene and the origin of replication
sequence from the Escherichia coli plasmid
pBR325. Replication in filamentous fungi is
made possible by the ansl sequence, which was
isolated by following procedures employed for
the ARS sequences of yeast. The Pyr4 gene
of Neurospora is used as a selection marker.
However, several Aspergillus genes that match
available mutants are now available and are be-
ing used in the development of vectors. The
rate of transfer of DNA into the fungi (i.e.,
the transformation frequency) is high (5000
transformants/µg of DNA); most of the trans-
formants are mitotically stable, indicating chro-
mosomal integration.
Promoter Systems. A number of As-
pergillus and Neurospora genes have been iso-
lated, and their regulatory sequences are cur-
rently under investigation. The most sucessful
application to date has been use of the glu-
coamylase promoter for the expression of bovine
18 Genetic Engineering
chymosin in A. nidulans [110]. Glucoamylase
promoter is induced by the presence of starch in
the growth medium. The chymosin so produced
was cleaved faithfully, with at least 90 % of
the product being secreted efficiently. Although
new, the filamentous fungi hold great promise
as efficient secretors. However, a great deal of
groundwork is still required, especially in the
areas of vectorology and regulatory signals in
order to exploit the full potential of this system.
4.3. Heterologous Gene Expression in
Higher Eukaryotes
4.3.1. Mammalian Cells
Gene expression in mammalian cell cultures has
an advantage over both the prokaryotic and the
lower eukaryotic systems because it yields a
product that most closely resembles the natu-
ral protein. Recombinant proteins expressed in
mammalian cells are likely to be more prop-
erly glycosylated, assembled, and folded to yield
functional proteins (post-translational modifica-
tion). One of the major drawbacks of using mam-
malian cells as host organisms was considered to
be the high cost involved in growing various cell
lines. Extensive work has gone into developing
cheaper culture media, and modern cell-culture
technology is highly amenable to scaleup. For
proteins such as erythropoietin, in which the ac-
tivity is closely linked to glycosylation [111],
expression in mammalian cells is the only avail-
able recourse. Also, Escherichia coli may not ef-
ficiently express extremely large molecules such
as blood factor VIII or tissue plasminogen ac-
tivator; therefore, these molecules are best ex-
pressed in mammalian cell lines. So far, almost
every cell line used has shown faithful mRNA
processing; i.e., the precursor mRNA is correctly
spliced to yield the expected mRNA. When cD-
NAs with their signal sequences are cloned,
faithful cleavage of the precursor protein and
efficient secretion rates have been obtained.
The significance of glycosylation has still not
been resolved. Glycosylation patterns appear to
vary from one cell line to another. How critical
is glycosylation of a protein to its functional-
ity? What are the implications of altered gly-
cosylation patterns? These questions have not
yet been answered definitively. Many proteins
that are glycosylated in their native state function
equally well as unglycosylated forms expressed
in E. coli [112], [113]. However, for some pro-
teins such as erythropoietin, glycosylation is es-
sential for bioactivity and alteration of the gly-
cosylation pattern affects the range of bioactvity
[114]. Furthermore, some cell lines cannot carry
out all the different kinds of post-translational
modifications. For example, several commonly
used mammalian cell lines do not efficiently per-
form the γ-carboxylation step required by blood
factor IX [115].
4.3.1.1. Vectors
Higher eukaryotes do not carry extrachromo-
somal (episomal) DNA molecules equivalent
to bacterial plasmids. Most vectors are derived
from eukaryotic DNA viruses or retroviruses.
Vectors Based on DNA Viruses. All eu-
karyotic vectors fall within two classes: inte-
grating (intrachromosomal) or episomal (extra-
chromosomal).
Integrating Vectors. The most popular inte-
grating vectors are derived from the simian
virus SV40, a widely studied double-stranded
DNA polyoma virus [116]. These shuttle vec-
tors contain sequences from the bacterial plas-
mid pBR322 that allow replication and segre-
gation in Escherichia coli. The SV40 sequences
consist of a promoter unit, an intervening se-
quence, and a polyadenylation site. The cDNA
to be expressed is cloned adjacent to the SV40
early promoter. A variation of this vector con-
taining the gene for the SV40 T antigen (Tag)
is also available [116]. The Tag is involved in
SV40 DNA replication and promotes transient
replication of vectors containing the SV40 ori-
gin. After transfection into COS-7 cells, the
plasmid replicates rapidly. Due to the increased
gene dosage, most heterologous proteins are ex-
pressed at easily detectable levels. This provides
a quick method of screening recombinant clones
within 72 h whereas 2 – 3 weeks are required
with stable transformants that arise by random
integration of the plasmid into the host genome.
The COS-7 monkey cell line has the Tag inte-
grated in its genome and is a popular cell line
for transient transfections [117].

Episomal Vectors. The following are major
advantages of an episomal vector:
1) Discrepancies or aberrations in expression of
cloned genes resulting from random indis-
criminate integration into the host genome
can be avoided.
2) A standardized environment is available for
comparison of related genes or their mutants.
3) A higher level of gene expression may be
obtained due to the multicopy nature of the
plasmid.
Of the episomal vectors, those based on the
bovine papilloma virus (BPV) have been studied
extensively. The BPV DNA is a circular duplex
about 8 kb in length which is maintained epi-
somally at about 100 copies per cell [118]. It
can transform mouse, rat, and hamster cell lines
and give rise to foci that can be visually scored
[119]. A 69 % subgenomic fragment of BPV is
sufficient to achieve transformation in the mouse
fibroblast cell line C127 [120]. The plasmid is
maintained in an episomal state.
Recombinant vectors have been constructed
from this fragment and the plasmid pBR322
or pML-2, and are widely used for expression
of heterologous genes [121]. If the vector con-
taining the heterologous gene is maintained epi-
somally, the copy number is generally low [121].
Although the BPV virus exists as an episome in
its native state, the presence of a heterologous
gene in the BPV vector may result in its integra-
tion into the host chromosome. The BPV vector
has been used in conjunction with the metallo-
thionein promoter to express biologically active
dimeric human choriogonadotropin [122].
Bovine kidney virus (BKV) based vectors
have also been employed to achieve high-level
expression of heterologous genes in an episomal
state [123].
The prospects for developing stable, nonin-
tegrating plasmids may also receive an impetus
from the discovery of indigenous episomal el-
ements (L factors) in certain mammalian cell
lines [124]. The L factors are circular duplex
molecules that appear to have their own ori-
gins of replication. Whether they will maintain
these characteristics after introduction of het-
erologous sequences remains to be seen.
Retroviral Vectors. A retrovirus has a RNA
genome that acts as a template for DNA synthe-
Genetic Engineering 19
sis. The intermediate DNA is then used as a tem-
plate for mRNA transcription. The demonstra-
tion that cloned retroviral DNA can produce in-
fectious virus particles (virions) on transfection
into cultured cells set the stage for their use as
vectors [125]. Retroviruses have several advan-
tages over DNA viruses. Integration of retrovi-
ral DNA into the host chromosome is obligatory
for their reproduction and is carried out very effi-
ciently. The long terminal repeat (LTRs) contain
all the necessary information required in cis (i.e.,
on the same strand of the RNA genome) for tran-
scription, replication, and integration [126]. The
rest of the viral DNA can, therefore, be replaced
by foreign DNA. By using a helper cell line to
supply other viral functions in trans (i.e., from
an independent genome), an infectious virion
can be produced. In the case of murine leukemia
virus (MLV) based vectors, two types of helper
cell lines are available: those that produce a mix-
ture of wild-type and recombinant virions, and
Ψ − mutants (the Ψ protein is required for the
packaging of wild-type virion DNA) which pro-
duce only the recombinant virions. Retroviruses
are capable of infecting various cell types; this
fact has been exploited to introduce extraneous
DNA sequences into bone marrow cells and em-
bryonic cells. Retroviral vectors have been used
to introduce cloned genes into cells both in cul-
ture and in vivo. Successful transfer of genes
into normal bone marrow cells and their subse-
quent transplantation into recipient animals have
been achieved [127]. Retroviruses are currently
used to create transgenic animals by infecting
preimplantation embryos [128]. With the recent
understanding of tissue-specific expression of
some mammalian promoters, the goal of tissue-
specific expression (e.g., in milk and pancreas)
has also been achieved [129], [130].
Most of the retroviral vectors are based on
Moloney murine sarcoma virus (Mo-MSV) and
Moloney murine leukemia virus (Mo-MLV).
Many of the vectors such as MVGT [131] and
M-MuLVneo [132] use the long terminal repeats
for direct transcription of the cloned gene and
the gpt and neo genes of Escherichia coli for
selection. Others, such as MLVtK and MMuLV-
SuTK-neo [133], carry additional promoters for
expression of cloned genes. Presence of the
SV40 origin of replication in the latter case al-
lows amplification in monkey COS cells.
20 Genetic Engineering
4.3.1.2. Promoters and Enhancers
A typical eukaryotic regulatory sequence con-
tains a promoter and enhancer(s). The promoter
guides the RNA polymerase to the correct ini-
tiation site for the eukaryotic messenger RNA.
A typical eukaryotic promoter is about 100 base
pairs (bp) long and consists of an AT-rich region
designated the TATA box. The TATA box is gen-
erally preceded by one or more upstream regu-
latory elements (UPEs), which are about 12 bp
in length and active in either direction. A well-
known example of a UPE is the CCAAT box.
The distance between the UPEs and the TATA
box is critical for the rate of transcription.
An enhancer is a cis-acting element of DNA
that stimulates transcription of adjacent genes
from the promoter in either direction and over
distances up to several kilobases. Viral en-
hancers were originally identified in SV40 and
polyoma viruses and, subsequently, in a vari-
ety of others [134]. In addition, enhancer se-
quences have also been identified in normal
cellular genes. Immunoglobulin enhancer se-
quences have been used to stimulate the tran-
scription of nearby genes cloned on plasmids in
lymphoid cells [135]. The ability of these se-
quences to stimulate transcription appears to be
nonspecific because they increase the transcrip-
tion of a number of different genes. The enhancer
element has also been linked to several genes
cloned in tandem, resulting in the high-level ex-
pression of all of them [136]. Both the enhancers
and UPEs must apparently be recognized by one
or more different soluble factors to elicit a full-
fledged response. Viral enhancer sequences such
as those of SV40 and adenovirus are active in
most cells, and the level of their activity can
be controlled by the availability of these fac-
tors. Some enhancers are inducible, for exam-
ple, by heat shock [137]. The metallothionein
enhancer is responsive to heavy metals [138],
the β-interferon enhancer responds to viral in-
duction [139], and elements in the long terminal
repeat of Mo-MLV [140] and Mo-MSV [141]
respond to steroids.
4.3.1.3. Chromosomal Gene Amplification
Plasmids containing sequences coding for di-
hydrofolate reductase (DHFR) are transfected
and integrated into the chromosomes of dhfr −
mutants of Chinese hamster ovary (CHO) cells
[142]. After selection of dhfr + clones, these
clones are placed under the selective pressure of
the toxin methotrexate (a competitive inhibitor
of DHFR), and the dhfr sequences undergo am-
plification (i.e., their copy number is increased
several hundredfold). Almost always, the cDNA
coding the recombinant protein of interest also
undergoes amplification (see also Fig. 7). The re-
sulting increase in gene dosage is accompanied
by a simultaneous increase in expression level.
This strategy has been employed successfully
for high-level expression of recombinant pro-
teins such as erythropoietin [143], blood factor
IX [144], and human β-interferon [145].
4.3.2. Insect Systems
The baculovirus Autographa californica nuclear
polyhedrosis virus (AcMNPCV) has been used
to express heterologous genes in insect cells cul-
tured from Spodoptera frugiperda. This virus
is nonpathogenic to mammals and plants, and
demonstrates a wide host range infecting at least
30 different Lepidoptera species. This system
is helper-independent and uses the highly ex-
pressed promoter of the A. californica coat pro-
tein, polyhedrin, for expression of foreign genes.
The level of expression obtained is consistently
higher than that in Escherichia coli, yeast, or
mammalian cells for a variety of genes [146].
Expression levels ranging from 1 to 500 mg/L
have been observed. The system is still in a
developmental phase, and several important is-
sues remain unresolved. Polyhedrin expression
varies depending on the cell lines infected and
the composition of the media. For example, S.
frugiperda cells accumulate high levels of poly-
hedrin, whereas the level produced by Bombyx
mori cells is at the detection limit [146]. Expres-
sion of different genes in this system often varies
widely. The effects of RNA structure, codon us-
age, and various control elements on gene ex-
pression are being investigated and may lead to
improvements in the near future.
One of the major issues is the quality of the
protein made by these systems. Insect cells ap-
pear to be extremely versatile in their ability to
carry out post-translational processes such as se-
cretion [147], localization in cellular organelles

[148] and at cell surfaces [149], proteolytic
cleavage [147], phosphorylation [148], N- and
O-linked glycosylation [147], [148], myristyla-
tion, and palmitylation [149]. Proteins such as
human interleukin-2 [150], human β-interferon
[147], and human α-interferon [151] have been
successfully expressed in this system. Human β-
interferon is glycosylated, the pre-β-interferon
signal peptide is removed, and the mature pro-
tein is efficiently secreted. Human interleukin-2,
however, is reported to be secreted in an ungly-
cosylated form [152]. Glycosylation with carbo-
hydrates such as sialic acid, galactose, and fu-
cose may turn out to be inefficient in insect sys-
tems [146], especially in mosquito cell lines such
as Aedes aegypti and A. albopictus. Efforts have
also been directed at developing a modified bac-
ulovirus for direct introduction into live cater-
pillars. Expression levels are extremely high in
this system, and it may prove to be a feasible
economical alternative to cell culture [153].
4.3.3. Plant Systems
The availability of Ti (tumor-inducing) plasmid
vectors opened up the possibility of studying ge-
netic regulation at a molecular level in plants.
Plant systems are adept at processing RNA, car-
rying out post-translational modification, and
targeting proteins to their specific subcellular lo-
cations [154].
4.3.3.1. Plasmid Vectors
Development of efficient vectors for the intro-
duction of DNA sequences into plants has been
achieved primarily through the use of the Ti plas-
mid of the soil bacterium Agrobacterium tume-
faciens [155]. This phytopathogen has evolved
a sophisticated method of infecting its plant
host cells in which a region of the Ti plas-
mid called T-DNA is integrated into the plant
genome resulting in two specific physiological
alterations: (1) diversion of carbon and nitro-
gen supplies for synthesis of derivatives of basic
amino acids called opines that A. tumefaciens
specifically catabolizes [156] and (2) prolifer-
ation of a tumor called crown gall [157]. The
T region (T-DNA) of the plasmid contains the
tumor-inducing genes [158], whereas the T-vir
Genetic Engineering 21
region is responsible for insertion of the plas-
mid DNA into the host genome [159]. Thus, any
foreign DNA inserted in the T region is cotrans-
ferred to the plant cells.
Several approaches to introduce genes into
plants have been pursued. Because A. tumefa-
ciens cannot easily be transformed by naked
DNA, alternative strategies had to be developed.
Early methods involved insertion of DNA into a
transposon such as Tn5 or Tn7 carried on a broad
host-range plasmid in Escherichia coli. Trans-
posons are mobile genetic elements that move
from site to site in a bacterial, yeast, or mam-
malian genome. The selection of the introduced
DNA segment was assured by a cumbersome,
time-consuming “homogenotization” procedure
[160]. Alternative vectors, such as the cointe-
grating and binary vectors, were developed to
circumvent these problems.
An example of a cointegrating vector is the
plasmid pMON200 which carries the pBR322
origin of replication and a selection marker, i.e.,
a Tn7-derived spectinomycin – streptomycin re-
sistance gene [155]. A triparental mating proce-
dure is used to transfer the new DNA into A.
tumefaciens. Only the essential regions of T-
DNA responsible for integration are retained;
the T-DNA regions responsible for tumor forma-
tion are eliminated. Agrobacterium tumefaciens
3111-SE cells carrying the “disarmed” T-DNA
plasmid pTi B6S3-SE are mixed with E. coli
carrying modified pMN200 and E. coli carry-
ing a helper plasmid pRK2013. The helper plas-
mid provides factors in trans that help to mobi-
lize pMN200 into A. tumefaciens. The mixture
is incubated overnight and then spread on a plate
carrying a mixture of spectinomycin and strep-
tomycin to select for the cointegrate plasmid that
arises by homologous recombination with the Ti
plasmid [161].
Cointegration into the Ti plasmid is an oblig-
atory step for the replication of pMON200.
The binary vector system yields stable trans-
formants [162], [163]. Both the T region and the
vir region can be isolated from the Ti plasmid
without loss of function. Therefore, the T-DNA
can be manipulated in E. coli and then trans-
formed into A. tumefaciens with a helper plas-
mid that carries the vir region. The presence of a
complete T region is not essential for function-
ing of the binary vector system. In binary vectors
such as pMON505 [164], the LIH region is re-
22 Genetic Engineering
placed by the origin of replication derived from
the broad host range plasmid pRK290. “Dis-
armed” T region DNA is equally efficient. Trans-
fer into Agrobacterium cells is carried out either
by transformation or by a triparental mating pro-
cedure using the mobilization helper plasmid as
described above.
Gene transfer into plant cells can be carried
out by infecting A. tumefaciens plant wounds
with cultures of A. tumefaciens carrying recom-
binant Ti plasmids [165]. Direct DNA trans-
fer into plant protoplasts can also be carried
out by using transformation [166], electropora-
tion [167], liposome fusion [168], microinjec-
tion [169], and leaf disk transfer [170] meth-
ods. The great advantage of gene transfer into
plant protoplasts is that the transformed cells can
be regenerated to give whole plants. This pro-
vides a powerful tool for carrying out genetic
and molecular analysis of transgenic plants and
their progeny.
The major advantage of the Ti system is its
broad host range. It can induce tumors in most
dicotyledonous species. In monocotyledonous
plants, DNA transfer and integration take place,
but no tumors are formed.
Naked DNA can be used to transform pro-
toplasts derived from monocotyledons and di-
cotyledons. However, the DNA is scrambled, re-
sulting in incomplete or rearranged copies [171].
Furthermore, plants cannot always be regener-
ated from protoplasts. Important issues still to
be resolved include the effect of integration site
on expression; the establishment of site-directed
integration systems analogous to those available
for yeast, and conversion of a Ti plasmid into an
episomal vector by introduction of centromeres,
plant autonomously replicating sequences, dom-
inant selection markers, and regulatory promoter
systems for expressing genes in specific cell or
tissue types.
4.3.3.2. Plant Promoters
The most commonly used plant promoter is the
nopaline synthase (nos) promoter [172]. Plant
promoters possess the familiar TATA box found
in most other eukaryotic promoters. Most plant
genes placed under their normal promoters are
fully active. Many of the promoters are specifi-
cally inducible; for example, a short, highly con-
served, sequence of 33 base pairs appears to
be responsible for the light inducibility of the
gene encoding ribulose 1,5-bisphosphate car-
boxylase in the pea [173]. Similarly, signals
that direct tissue-specific expression of the β-
phaseolin gene of bean are localized to a 800-bp
region at the 5
end of the gene [174]. Many
of these genetic regulatory pathways are being
elucidated and offer the potential of using in-
ducible systems to express cloned genes in a
tissue-specific fashion.
5. Applications of Recombinant DNA
Technology
5.1. Therapeutic Agents
The largest impact of the technological revolu-
tion produced by genetic engineering has been
on the pharmaceutical industry. Almost every
major pharmaceutical house was immediately
attracted by the possibility of generating unlim-
ited quantities of rare, valuable, therapeutically
important proteins. This also led to a highly pro-
ductive liaison between academia and industry.
Distinguished scientists have joined forces with
industrial firms to realize the commercialization
of an academic research project in an industrial
setting. However, while the replacement or im-
provement of traditional drug manufacture is at-
tractive, it also requires standardization of cell
growth and fermentation processes, as well as
training of personnel to handle downstream pro-
cessing and purification. Many of the compa-
nies concerned have invested substantial cap-
ital in this area. In addition to developing in-
house capabilities, most of them also liaise with
smaller biotechnology companies via contract
research and product licenses. Although genetic
engineering has simplified the manufacture of
several established therapeutics such as insulin,
growth hormone, serum albumin, and clotting
factors, that were previously produced through
purification from source tissues, it has also pro-
vided a host of new molecules that have substan-
tial promise of being therapeutically important.
In addition, development of safer vaccines de-
rived from antigenic determinants such as sur-
face proteins of pathogenic organisms has also
become possible. The technology may also be

extended to enhance processes used for every-
day pharmaceutical products such as vitamins,
steroids, antibiotics, and other bioactive pep-
tides.
Thus far (1988), four genetically engineered
drugs have been approved for the United States
market by the FDA, namely, human insulin, hu-
man growth hormone, human α-interferon, and
tissue plasminogen activator.
Insulin derived from porcine or bovine
sources was an already established product in the
worldwide market for diabetes treatment. The
cloned product was developed by Eli Lilly in
collaboration with Genentech by using an Es-
cherichia coli expression system [175]. The in-
sulin produced by traditional methods is inex-
pensive and does not have immunogenic toler-
ance problems. However, submitting recombi-
nant insulin for FDA approval provided indus-
try with the experience needed in obtaining ap-
proval for other recombinant DNA products. For
a detailed description of insulin, see → Peptide
and Protein Hormones.
Interferon was discovered as an antiviral
agent [176]. Leukocyte interferons constitute a
multigene family, for detailed information see
→ Interferons [177]. The production of various
interferons depends on the nature of infection;
not all of them are induced at the same time.
The first interferon to be cloned was human
leukocyte interferon α-1 [178], followed almost
immediately by human leukocyte interferon α-
2. Interferon α-2 exhibited a more dramatic an-
tiviral activity in human cells than interferon α-
1 which was more potent in bovine cells [179].
Both Hoffman La Roche and Schering Plough
proceeded with the expression of human inter-
feron α-2 in Escherichia coli. In 1986, inter-
feron was approved by the FDA for use against
hairy cell leukemia in the United States and other
countries such as the United Kingdom, the Fed-
eral Republic of Germany, France, Italy, and
Canada. It is also approved for the treatment of
Kaposi’s sarcoma in the United States, Austria,
Denmark, Switzerland, France, and the United
Kingdom, as well as for multiple myeloma and
condyloma acuminatum in Denmark, Portugal,
Ireland, and Argentina.
The complexity of the interferon system was
unknown at the time of its discovery. There-
Genetic Engineering 23
fore, cloning of the first interferon was hailed
worldwide as a major breakthrough in medi-
cal science. Interferon was likened to penicillin
as a broad-spectrum antiviral agent. Cloning of
the first interferon led to the discovery that in-
terferons are a finely tuned, complex, intricate
network of molecules acting either in concert
or independently to combat viral infections and
modulate immune response. Besides hairy cell
leukemia, human interferon α-2 may be thera-
peutically potent against renal cell carcinoma,
warts, and multiple myelomas. Human infec-
tions caused by viruses, such as rhinovirus, her-
pes (eye and generalized infections), adenovirus
(eye infections), papilloma virus, and hepatitis B
virus, are also responsive to interferon treatment.
Growing evidence indicates that this complex
system may also protect the human body against
certain bacterial and protozoan infections [180].
Human tissue plasminogen activator (t-
PA) is a protein with a clear-cut function and
is one of the most effective agents in dissolv-
ing blood clots. The protein is a multidomain
serine protease that converts plasminogen to
plasmin, which in turn lyses the fibrin network,
thus helping to maintain hemostasis (→ Blood,
Chap. 2.2.3.) [181]. It promises to be an ef-
fective therapeutic agent for thrombolysis in
myocardial infarction, deep vein thrombosis,
and similar indications. The cDNA for t-PA was
cloned and expressed in CHO cells by Genen-
tech using the DHFR amplification system (see
Section 4.3.1.3.) [182]. Tissue plasminogen ac-
tivator must be produced in mammalian cell
lines because of its large size and extensive
glycosylation. Clinical studies demonstrate de-
creased reocclusion rates and lower incidence
of bleeding complications in patients treated
with recombinant t-PA in comparison to other
thrombolytic agents such as streptokinase [183].
Despite initial rejection, by late 1987 Genentech
succeeded in gaining approval for t-PA in the
United Kingdom, the United States, and Canada.
The systemic half-life of t-PA in humans is
only 2 –5 min [184]. The efficacious therapeutic
dose in humans is, therefore, high and exceeds
100 mg [183]. This causes proteolysis of plasma
proteins. A t-PA molecule with a longer half-
life could overcome these problems and reduce
the production cost per therapeutic dose. Several
companies aimed to genetically engineering t-
24 Genetic Engineering
PA to obtain a second-generation molecule with
a longer half-life [185].
Human growth hormone was one of the
earliest therapeutically important genes to be
cloned [186]. Cloning allowed replacement of
the tedious and cumbersome methodology in-
volved in purifying this protein from pituitary
gland. Genentech’s application for the ther-
apeutic use of human growth hormone was
awarded by the FDA in 1986. The FDA also
granted approval to Eli Lilly for a modified ver-
sion of the hormone that lacked the N-terminal
methionine residue. This modified hormone is
claimed to reduce the antigenic problems posed
by the Genentech product, which retains the N-
terminal methionine. For a detailed description
of growth hormone, see → Peptide and Protein
Hormones.
Development of New Products. Erythro-
poietin is a hormone that stimulates precursor
bone marrow cells to differentiate into red blood
cells. Trials with recombinant erythropoietin in-
dicate positive results for treatment of renal
disease associated with anemia [187]. Further-
more, it may also be useful for treating sickle cell
anemia, an inherited disorder of the red blood
cell [188]. Colony stimulating factors are also
generating strong interest in the treatment of sev-
eral hematopoietic deficiencies [189]. Several of
these have been cloned and are at various stages
of development. Granulocyte colony stimulating
factor ( G-CSF) [190], granulocyte macrophage
colony stimulating factor ( GM-CSF) [191],
macrophage colony stimulating factor ( M-CSF
or CSFI) [192], interleukin-3 (multi-CSF) [193],
and interleukin-4 ( B-cell stimulating factor 1)
[194] are all being developed as products that
could restore immunocompetence when used as
an adjunct to chemotherapy. By the same cri-
teria, these factors could prove to be extremely
useful in treatment of systemic infections or
burns and in bone marrow transplantation.
Interleukin-2 (IL-2) is also in advanced
stages of testing, especially for cancer therapy
in combination with lymphokine-activated killer
cells or tumor-infiltrating lymphocytes. As with
the interferons, the cloning of several of the cy-
tokines has shed light on their role in the body’s
immune defense system. Interleukin-2, for ex-
ample, appears to be the major inducer of γ-
interferon. Interleukin-1, tumor necrosis factor,
and γ-interferon are believed to play a role in
several human diseases such as arthritis, dia-
betes, and atherosclerosis [195]. Therefore, in-
terest exists in using the cloned products to set
up screens for antagonist molecules.
Other products in the developmental stage
are growth factors such as the platelet derived
growth factor (PDGF), epidermal growth fac-
tor (EGF), and fibroblast growth factor (FGF)
mainly in the areas of wound healing and an-
giogenesis. Blood clotting factors, such as tis-
sue factor and factors VII, VIII, and IX, have
been cloned and are in the developmental stage.
Factor VIII is already being studied in clini-
cal trials for inducing clotting in hemophiliacs
[196]. Hormones such as thrombopoietin, fol-
licle stimulating hormone [197], gonadotropin
[198], and somatotropin [199] have been cloned
and are currently being investigated (→ Peptide
and Protein Hormones).
5.2. Vaccines
Control of deadly diseases such as smallpox,
cholera, and polio can be attributed mainly to
vaccines. For a detailed description of vaccines,
see → Immunotherapy and Vaccines. Conven-
tional methods of vaccine production have saved
millions of lives. Despite the large market for
vaccines, few companies have entered the field
because they are intimidated by the immense
legal costs. Genetic engineering, however, pro-
vides a safe alternative because it rules out vacci-
nation by live or attenuated organisms and also
offers the possibility of producing vaccines to
control diseases that are beyond the scope of
traditional methodology. Isolated gene products,
especially surface antigens, can elicit an immune
response from the body.
Several vaccines for use in humans are cur-
rently being investigated, some of the more im-
portant being those against hepatitis B, malaria,
polio, herpes, gonorrhea, influenza, leprosy, and
acquired immune deficiency syndrome (AIDS).
Hepatitis B Vaccine. The hepatitis B vac-
cine is the first genetically engineered vaccine
to enter the U.S. market. The vaccine is pro-
duced by expressing the cloned hepatitis B virus
surface antigen (HbsAg) in Escherichia coli and

yeast. The product physically and antigenically
resembles the virus particles found in the serum
of infected patients [200], [201]. Its efficacy as
an immunization agent against hepatitis B in-
fection was demonstrated in both chimpanzees
[202] and humans [203].
Malaria Vaccine. The malaria vaccine is a
prime example of what genetic engineering
can accomplish where conventional approaches
have failed. Because of the inherent antigenic
diversity of the malaria parasite, the whole or-
ganism cannot be used as a source of vaccine.
Cloning of some of the genes of this parasite
has shown that some gene products may be in-
variant and, therefore, suitable candidates for a
vaccine. An example of one such apparently in-
variant protein is the repeat sequence epitope
from the circumsporozoite gene of Plasmodium
falciparum [204]. A vaccine based on this se-
quence is currently undergoing clinical trials. If
successful, it will replace or augment methods
such as mosquito control and chemotherapy that
are currently used to check the spread of this dis-
ease.
Acquired Immune Deficiency Syndrome.
Acquired immune deficiency syndrome ( AIDS)
is caused by a retrovirus called the human im-
munodeficiency virus (HIV), which has been
cloned and sequenced [205]. The virus is spread
via body fluids, mostly by sexual intercourse
or the use of contaminated syringes and nee-
dles among drug addicts. The alarming rate at
which this fatal disease is spreading has caused
great anxiety in the world health and medical
community. AIDS has become the world’s most
deadly infectious disease, ranking fourth after
ischemic heart disease, strokes and acute res-
piratory infections in terms of mortalities (2.28
million deaths worldwide in 1998).
A number of pharmaceutical and biotechnol-
ogy firms are working closely with academic in-
stitutions to find methods to control this disease.
A synthetic peptide fragment, encompassing the
amino acid sequence from residues 735 to 752
of the viral envelope protein subunit gp41 was
used to produce antibodies. The resulting anti-
serum reacted with the envelope subunit [206],
indicating that viral envelope proteins are very
immunogenic and may be used as a vaccine. A
vaccine based on the recombinant version of the
Genetic Engineering 25
AIDS surface antigen protein gp160 produced
in insect cells is already undergoing clinical tri-
als [207]. The gp120 envelope protein of HIV-1
is also a prime target for use as a vaccine. An-
other approach is being followed by Smith Kline
and French Laboratories and Genentech to de-
velop an AIDS vaccine. Here, “soluble receptor”
molecules are used that bind tightly to the virus,
thus preventing its interaction with a lymphocyte
or a brain cell [208].
Polio Vaccine. A novel approach has been
used by Connaught Research Laboratories to
develop a candidate polio vaccine [209]. An
antigenic epitope for poliovirus type 3 was in-
serted into the 3
end of the tobacco mosaic
virus coat protein and expressed in Escherichia
coli. Assembly of this protein was expected to
produce a highly immunogenic, high molecular
mass complex that carries several copies of the
antigenic epitope. When injected into rats, this
complex elicited a strong immune response that
induced formation of neutralizing antibodies to
poliovirus [209].
Other Vaccines. Production of vaccines via
genetic engineering provides a method of ob-
taining proteins that undergo correct post-
translational modification (e.g., glycosylation)
by expressing them in mammalian cell lines.
These modifications may be required for the pro-
tein to attain its native configuration. This is true
in the case of the herpes simplex virus glycopro-
tein D, which when expressed in Chinese ham-
ster ovary cells [210] can protect guinea pigs
against genital viral infection.
Vaccinia virus vectors for polyvalent vac-
cines have also been developed [211]. Although
this approach may allow one-shot immuniza-
tion against several diseases, it is not without
risk, because wide-scale use may elicit a severe
response in patients with low immunocompe-
tence. The safest vaccines are those that con-
tain no DNA whatsoever, and the only way to
achieve this is through synthetic and genetically
engineered vaccines.
5.3. Genetically Altered Organisms
5.3.1. Transgenic Animals
Introduction of the human growth hormone gene
under the control of metallothionein promoters
26 Genetic Engineering
in mice was accomplished in 1983 [212]. This
experiment caused a sensation because the mice
inheriting the gene were much larger in size than
control animals. Two methods are employed for
introduction of foreign DNA into the fertilized
mouse egg: (1) retroviral-mediated transfer and
(2) direct microinjection into the male pronu-
cleus of the fertilized egg. The DNA is integrated
randomly and may form concatemers. Improved
methods for targeting DNA to specific sites in
the chromosome are still being perfected. Trans-
genic mice are widely used to study DNA se-
quences that mediate tissue- or cell-specific gene
expression [137], [138]. In addition, they are em-
ployed as a routine tool to study oncogenes [213]
and to set up animal models for genetically de-
termined disease states [214].
The success achieved with transgenic mice
promoted experiments with other animals such
as fish [215], rabbits, sheep, and pigs [216], with
a view to carrying out studies in improvement
of livestock. One of the earliest experiments uti-
lized human growth hormone in pigs. Despite
high expression of the gene, no evidence of en-
hanced growth appeared [217]. Instead, the pigs
developed arthritis-like symptoms. Growth hor-
mone is normally produced in a highly regu-
lated fashion by the pituitary gland. The devel-
opment of pathological conditions was probably
due to unregulated expression of the gene in all
tissue types. When porcine growth hormone is
expressed in a regulated fashion in transgenic
pigs, their rate of growth is increased substan-
tially. Furthermore, the meat is lean. Steps are
being taken to commercialize breeding lines of
such transgenic pigs [218].
The fertility of Booroola merino sheep in-
creased severalfold upon introduction of the fer-
tility (F) gene into transgenic sheep [218].
The latest use of transgenic animals has been
in the production of heterologous proteins in
milk. Using promoters of genes coding for milk-
specific proteins (e.g., β-lactoglobulin and whey
acid protein), researchers have expressed blood
factor IX [219] and t-PA [129] in the milk of
transgenic sheep and mice, respectively. Sheep
β-lactoglobulin has also been expressed in trans-
genic mice, which produced up to 23 mg/mL of
β-lactoglobulin in their milk [219].
Transgenic animals may soon become an at-
tractive alternative for the production of genet-
ically engineered, biologically active proteins.
Several regulatory issues would have to be re-
solved, but expression levels and the quality of
the product may excel those achieved via con-
ventional methods.
5.3.2. Transgenic Plants
The concept of manipulating plant genetics has
direct appeal for the agricultural industry. It pro-
vides a tool for introducing specific genes to pro-
tect plants against potentially lethal agents such
as herbicides, viruses, and insects. Other advan-
tages include the improvement of crop yield and
quality.
The development of plasmid vectors carry-
ing selectable markers for tranformation of plant
cells brought about a revolution in plant breed-
ing. By using the soil bacterium Agrobacterium
tumefaciens with its associated Ti plasmid as a
vector (cf. Section 4.3.3.1.), several transgenic
strains of plants were generated. Kanamycin
resistance carried on the A. tumefaciens plas-
mid is inherited stably in progeny of transgenic
plants [154]. The host range of the A. tumefa-
ciens is quite large among the dicotyledonous
species ranging from petunias [220] to pines
(e.g., the Douglas fir [221]), deciduous species
(e.g., poplar [222]), and cotton [223]. Trans-
fer of single gene traits has met with consid-
erable success. Transgenic tobacco plants that
carried a mutant aro A gene from Salmonella
typhimurium conferred tolerance to the herbi-
cide glyphosate [224]. The aro A locus codes
for 5-enolpyruvyl-3-phosphokimate synthetase
which is inhibited by the herbicide glyphosate.
The mutant enzyme is resistant to the herbi-
cide. By engineering a Streptomyces acetylating
enzyme gene into tobacco, tomato, and potato
plants, resistance to the herbicide Basta has been
achieved [220]. Acetylation of the herbicide ren-
ders it ineffective. Resistance to tobacco mosaic
virus was achieved in tomato and tobacco plants
that were engineered to carry tobacco mosaic
virus coat protein [225]. The presence of the coat
protein provides cross-protection against super-
infecting viruses because it encapsidates (pack-
ages) the viral RNA and renders it noninfectious.
Another route to achieving viral resistance has
been through transformation of tobacco plants
with a satellite RNA species derived from a be-
nign strain of cucumber mosaic virus. The pres-

ence of this RNA protects the plant from viru-
lent infection [226]. Resistance against several
insect pests has been achieved by creation of
transgenic plants carrying a gene encoding cow-
pea trypsin inhibitor [227]. Proteinase inhibitors
defend plants by inhibiting the proteolytic activ-
ity of the pathogens; the pathogens require this
activity for the breakdown of plant protein and
thus for their nutrition.
Direct transfer of naked DNA into proto-
plasts has also been employed in plant species
that do not fall within the host range of A.
tumefaciens [173]. This method is used partic-
ularly for monocotyledonous species, includ-
ing cereals, which constitute the most impor-
tant group of plants providing nutritional needs
in humans. Protoplast fusion [228], liposome-
mediated DNA transfer [229], and electropora-
tion [230] have been used to transform these
plant cells. Problems concerning the success-
ful regeneration of plants from protoplasts have
been partially solved, at least in the case of rice
[231]. Attempts to repeat this success with other
cereals such as maize, wheat, and barley are un-
der way.
Although transfer of single gene traits has
been accomplished successfully, many desirable
traits such as disease resistance, stress toler-
ance, and photosynthetic efficiency probably de-
pend on the activity of several genes. Intensive
effort must, therefore, be mounted to charac-
terize these genes. The availability of vectors,
improved methods of gene transfer, and im-
provement in plant regeneration techniques have
opened the door to what may be a revolution in
plant breeding.
5.4. Gene Therapy
Gene therapy is considered by many to be the ul-
timate frontier still to be conquered by recombi-
nant DNA technology. Despite intense research,
progress has been slow. Gene therapy, as cur-
rently envisaged, differs from creation of trans-
genic animals in that it involves somatic gene
manipulation as opposed to germ line manipu-
lation. Work thus far has been restricted to labo-
ratory animals. Approaches used for gene trans-
fer include retroviral-mediated transfer [232],
microinjection [233], electroporation [234], up-
take of DNA precipitated by calcium phosphate
Genetic Engineering 27
[233], and homologous recombination [235].
The most popular of these methods is retroviral
transfer. Concern exists over the use of retroviral
vectors, and they must be shown not to pose a
cancer hazard as a result of either recombination
events or random insertion into (and activation
of) oncogenes.
Hemopoietic stem cells have been the favorite
candidates for gene transfer experiments. After
retroviral transduction, the cells are transplanted
into mice that have been lethally irradiated to
eliminate existing stem cells. Expression of the
introduced gene is checked four to six months
later to allow for differentiation of stem cells
[236]. Another method utilizes cultured murine
fibroblasts; the cells are transfected with the de-
sired DNA and implanted at several anatomical
sites [237]. Expression of the gene of interest
can potentially be regulated, depending on the
site of implantation. This type of implantation
has been termed “transkaryotic implantation.”
Most of the early experiments used the retro-
viral LTRs for expression of the foreign DNA.
The major problem has been low expression in
the reconstituted cells. The LTR-based expres-
sion seems to be irreversibly blocked, especially
in bone marrow cells. A breakthrough has been
achieved [238]. A retroviral vector carrying the
β-globin gene under the control of its natural
promoter was transfected into hemopoietic stem
cells. Measurable quantities of β-globin were
found in all mice that had undergone bone mar-
row transplantation. These results illustrate the
importance of the choice of promoters to achieve
tissue-specific expression.
The aim of the above studies is to provide
basic knowledge so that experimentation can be
extended to humans. The most obvious candi-
dates for gene therapy in humans are genetic
hemoglobin disorders, the best known and most
commonly inherited human diseases. Other can-
didates are diseases caused by inborn errors
of metabolism such as the Lesch – Nyhan syn-
drome, which is due to a deficiency of hypo-
xanthine phosphoribosyltransferase, and severe
combined immune deficiency syndrome, which
is caused by defective production of adenosine
deaminase.
Gene therapy is still viewed with skepticism
and concern by the public. The FDA and the NIH
Recombinant DNA Advisory Committee intend
to scrutinize all gene therapy proposals closely
28 Genetic Engineering
prior to approval [239]. However, the follow-
ing criteria proposed by Mulligan may help
researchers choose a disease suitable for gene
therapy [240]:
1) The disease must be life-threatening and in-
curable.
2) The normal counterpart of the defective gene
must be isolatable.
3) The organ or tissue responsible for disease-
related pathophysiology must be identified.
4) Introduction of corrective sequences into a
significant fraction of the affected system
should be achievable.
5) The gene must be adequately expressed.
Although, in theory gene therapy should
work, this goal has not been achieved in reality.
The greatest detriments to progress have been in-
adequate expression levels, an inability to infect
large numbers of cells, and a lack of methods
for identifying the derived cell population in a
mixed population of cells.
5.5. Diagnostics
One of the offshoots of streamlining DNA hy-
bridization techniques is the establishment of di-
agnostics based on DNA probe technology. By
using the exquisite specificity with which com-
plementary sequences on single-stranded DNA
or RNA find each other, cloned gene fragments
are employed to detect infectious agents, hered-
itary markers, oncogenes, and antibiotic resis-
tance genes. Currently, efforts are focused on re-
placing labor-intensive, time-consuming DNA
hybridization methods with simpler and faster
techniques. This is essential for successful com-
mercialization of this technology, especially if
it is to compete favorably with the immunodi-
agnostic market. Several of the currently em-
ployed tests use radioactively labeled probes.
One of the first assays to be marketed was the
Salmonella detection assay that utilizes a ra-
dioactive probe [241]. Simplification of DNA
immobilization techniques and proprietary re-
actions that accelerate hybridization have helped
to reduce the time required for such assays. The
FDA approved the first isotopic probe in 1987
for the diagnosis of legionnaires’ disease by use
of patient specimens [241].
Because the use of radioactive isotopes is a
cause for concern, especially in clinical labora-
tories that handle thousands of samples, many
companies are trying to find nonisotopic tags.
Suitable alternatives include fluorophore-based
tests and enzymes linked to the probe either
directly or via a biotin – avidin complex. The
fluorophore-based tests are best suited to au-
tomation; inexpensive, easy-to-use fluorometers
are being developed. Enzyme-based assays use
dye conversion for detection, and these can
be read on colorimeter or spectrophotometer.
The low sensitivity of the nonisotopic meth-
ods presents a severe problem in that assay
time is prolonged because the samples often re-
quire further culturing. Cetus has developed a
selective DNA amplification technique called
the polymerase chain reaction (PCR) that can
amplify given DNA samples a million times
[242]. This method relies on the hybridization
of an oligomeric primer to a single-stranded
DNA molecule and the ability of the DNA poly-
merase to complete the synthesis of the second
strand. The double-stranded DNA is then dena-
tured, and the whole process is repeated sev-
eral times, resulting in a 200 000-fold amplifica-
tion of the DNA sequence. This could overcome
problems of low DNA content in samples and
has been shown to be effective for detection of
HIV-1 in DNA of peripheral blood mononuclear
cells [243]. Several companies are involved in
automating these assays.
Besides detecting infectious bacteria and
viruses, DNA probe technology provides the
means for diagnosing several inherited sin-
gle gene disorders. Genetic screening by this
method is based on analysis of restriction frag-
ment length polymorphism (RFLP). Polymor-
phism in the DNA sequence is quite high (one
in every 200 bp in the human genome). Because
of the variance in DNA sequence, recognition
sites for restriction endonucleases may also dif-
fer giving rise to altered patterns of restriction
fragment lengths. Distinctive RFLP patterns can
be linked to several genetic diseases such as tha-
lassemia [244] or insulin [245] and growth hor-
mone disorders [246]. The DNA from the pa-
tient’s blood is digested with a specific restric-
tion endonuclease, and the RFLP pattern is ob-
tained by hybridization with a marker gene. Be-
cause deletions or mutations within the gene can
produce an altered RFLP pattern, this type of

analysis can be used to predict the inheritance
of a disease. A number of RFLP markers asso-
ciated with specific diseases such as cystic fibro-
sis, sickle cell anemia, Duchenne-Type muscular
dystrophy, thalassemia, hemophilia, retinoblas-
toma, and Huntington’s chorea have been identi-
fied [247]. Some of these tests are available com-
mercially, but still expensive (cost ranging from
$ 800 to $ 1500) and time-consuming (8 – 10 d).
Tests are also available for Philadelphia chromo-
some, chronic myelogenous leukemia, and T- or
B-cell cancers.
6. Regulatory and Safety Aspects
Following the recommendations drawn up af-
ter the Asilomar meeting [248], the National
Institutes of Health (NIH) set up the Recom-
binant DNA Advisory Committee (NIH RAC)
in 1976. This committee proposed several lev-
els of biological containment for experiments
involving gene manipulation [249], with rigor-
ous containment procedures. In addition, Insti-
tutional Biosafety Committees (IBCs) were set
up by pharmaceutical companies and academic
institutions to govern the conduct of everyday re-
combinant DNA research. Today, most countries
involved in recombinant DNA research have
implemented nationally monitored programs to
control research in genetic engineering. Experi-
ence has shown that most genetic engineering
experiments pose no greater threat than does
conventional microbiological research. Conse-
quently, containment levels have been relaxed
in recent years. “High-risk” experiments such
as those involving cloning of toxins and lethal
viral genomes into harmless organisms are still
strictly regulated. A surge of activity occurred
in the study of transgenic animals. Some work
in this area has also necessitated establishment
of rigorous codes to prevent these animal pop-
ulations from entering the common gene pool.
For instance, the creation of transgenic mice car-
rying the entire genome of the AIDS virus has
caused concern [250]. As a result, stringent mea-
sures have been advocated to prevent accidental
release of these animals.
Another issue discussed frequently is the use
of recombinant products as therapeutic agents.
The main concern here is the authenticity of the
product. Many factors such as codon usage, gly-
Genetic Engineering 29
cosylation, post-translational modification, pro-
tein folding, and methionyl derivatives (heterol-
ogous proteins expressed cytoplasmically in Es-
cherichia coli that retain the N-terminal methio-
nine) can all change the functionality of a pro-
tein. Some changes may be apparent immedi-
ately, but others may escape notice because of
methodological limitations of the assay used.
An additional problem is the homogeneity of
the preparation. Rigorous control of purification
schemes used in the isolation of a recombinant
product is required. The final product should be
free of contaminants such as proteolytic frag-
ments, host pyrogens, and host nucleic acid,
which can elicit an immune respone in patients
[251]. This may be deleterious to the efficacy
of the drug or the general health of the patient.
Therefore, studies must determine whether the
resultant antibodies are specific, neutralizing, or
associated with hypersensitivity. The use of cell
lines and transgenic animals that synthesize the
desired protein as production hosts is proposed
as a method of overcoming these problems. De-
spite these problems, a number of recombinant
products such as insulin, α-interferon, human
growth hormone, and t-PA have made their way
into the market and are being used successfully.
The application of recombinant DNA tech-
nology in agriculture has created microbes that
protect plants from natural threats such as frost
and insect pests, as well as transgenic plants en-
gineered to withstand harmful herbicides and
viruses. Controversy over the release of such or-
ganisms into the environment has reached dra-
matic proportions. Of primary concern are the
mixing of gene pools in the environment and the
inadvertent introduction of such “hardy” char-
acteristics as herbicide resistance into “weedy”
plants, with disastrous consequences. The NIH
guidelines deal with the issue of field testing and
deliberate release of such organisms with great
caution on a case-by-case basis. The Environ-
mental Protection Agency also provides recom-
mendations in this case. Field tests for plants are
closely monitored to ensure that they are grown
in a controlled, isolated environment to prevent
cross-pollination or their permanent establish-
ment.
The benefits of engineered organisms for
agriculture, health, and environmental purposes
are obvious. The enormous promise of this tech-
nology is bound to be realized in coming years.
30 Genetic Engineering
As in the past, all new issues will have to be
addressed with prudence and wisdom so that ra-
tional guidelines for conducting such research
can be drawn up and the fears of the general
public can be allayed.
7. Glossary of Special Terms
amplification: generally refers to an increase in
the copy number of a gene (this can some-
times be induced by selection pressure, as
in DHFR-based amplification)
copy DNA: DNA strand synthesized on an
mRNA template by the enzyme reverse
transcriptase
cosmid: hybrid vector composed of part phage
and part plasmid
enhancer: DNA sequence that can increase
transcriptional initiation, sometimes even
at a considerable distance from the pro-
moter
episome: usually a double-stranded circular
DNA molecule that can exist extrachro-
mosomally within a cell
expression: generally refers to the biosynthesis
of a protein directed by cellular compo-
nents (mRNA, tRNA, ribosomes, etc.)
fusion protein: generally refers to a recombi-
nant protein expressed as part of a pro-
tein that is abundantly expressed in the
host organism (e.g., lac, Trp)
library: cDNA or genomic DNA, is a population
of chimeric DNA molecules representing
the genomic content or the mRNA con-
tent of a specific cell
ligation: the process that involves in vitro join-
ing of double-stranded DNA molecules
by the enzyme T4 DNA ligase
operon: cluster of genes that encode a spe-
cific biosynthetic pathway or function
(e.g., lactose, heat-shock, or tryptophan
operon)
phage: bacterial virus (e.g., λ, M13, T4, T7)
plasmid: double-stranded circular DNA
molecule that can exist extrachromoso-
mally and replicate autonomously
promoter: conserved sequence that is recog-
nized by the host-specific RNA polymer-
ase to initiate mRNA synthesis
replicon: an extrachromosomal DNA or RNA
molecule that can replicate independently
of the genome (automous replication)
repressor: protein molecule that can bind to a
specific conserved sequence, the operator
sequence, in certain promoter systems to
turn off transcription
restriction endonuclease: enzyme that recog-
nizes a specific sequence and catalyzes
the formation of cuts in double-stranded
DNA; used as a tool in genetic engineer-
ing
retrovirus: RNA virus that uses a DNA interme-
diate for replication
selection marker: gene such as drug resistance
or an auxotrophic requirement used to se-
lect for a plasmid in a particular host back-
ground
shuttle vector: plasmid that has the requisite
DNA sequences to permit its existence in
more than one host such as bacteria and
mammalian cell lines
transfection: introduction of naked DNA, gen-
erally of viral origin, into a cell
transformation: introduction of naked DNA,
generally of bacterial origin, into a cell
translation: step in protein biosynthesis that in-
volves the transfer of information from
mRNA into the synthesis of a protein
transposon: genetic element capable of moving
from site to site within a genome
8. References
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Genetic Engineering 31
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 Germanium and Germanium Compounds
Germanium and Germanium Compounds
Jean Scoyer, Metallurgie Hoboken-Overpelt, Olen, Belgium (Chaps. 1 – 10)
Hélian Guislain, Metallurgie Hoboken-Overpelt, Olen, Belgium (Chaps. 1 – 10)
H. Uwe Wolf, Abteilung Pharmakologie und Toxikologie, Universität Ulm, Federal Republic of Germany
(Chap. 11)
1. Introduction . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . .
3. Chemical Properties . . . . . . . . . .
4. Resources and Raw Materials . . . .
5. Production . . . . . . . . . . . . . . . .
5.1. Production of Germanium Concen-
trate . . . . . . . . . . . . . . . . . . . . .
5.1.1. Bleiberger Bergwerks Union . . . . . .
5.1.2. Jersey Minière Zinc . . . . . . . . . . .
5.1.3. Musto Exploration . . . . . . . . . . . .
5.1.4. Peñarroya . . . . . . . . . . . . . . . . . .
5.1.5. Pertusola . . . . . . . . . . . . . . . . . .
1. Introduction
Germanium [7440-56-4], Ge, atomic number
32, atomic mass 72.59, is a semiconducting el-
ement found in group 14 of the periodic table.
Germanium has five natural isotopes: 70 Ge
(20.53 %), 72 Ge (27.43 %), 73 Ge (7.76 %), 74 Ge
(36.54 %), and 76 Ge (7.76 %).
Germanium also has some radioactive iso-
topes with greatly different half-lifes, the iso-
tope with the longest half-life being 68 Ge (287
days).
In 1871, Mendeleev predicted the exis-
tence and the properties of an unknown element,
ekasilicon, to be placed between silicon and tin
in his periodic system of elements. In 1886,
Winkler isolated a new element from argy-
rodite, 4Ag2 S · GeS2 . This element, named ger-
manium, showed properties remarkably close to
those predicted by Mendeleev.
Germanium found its first industrial applica-
tion in 1947 with the development of the transis-
tor. Until the early 1970 s, it was used extensively
in the solid-state electronics industry, although it
has been replaced almost entirely by the cheaper
silicon.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a12 351
1
1 5.1.6. Other Primary Producers . . . . . . . . 7
2 5.2. Production of Germanium from
2 Germanium Concentrate . . . . . . . 7
3 5.3. Purification . . . . . . . . . . . . . . . . 8
4 5.4. Transformation Processes . . . . . . 8
6. Environmental Protection . . . . . . 9
5 7. Quality Specifications . . . . . . . . . 9
5 8. Chemical Analysis . . . . . . . . . . . 10
5 9. Storage and Transportation . . . . . 10
6 10. Uses and Economic Aspects . . . . . 10
6 11. Toxicology and Occupational Health 12
6 12. References . . . . . . . . . . . . . . . . . 13
The main use of metallic germanium cur-
rently is for infrared optics. Germanium tetra-
chloride is used in optical fiber production. Ger-
manium dioxide is used mainly as a catalyst in
the production of polyester and synthetic textile
fiber.
The total consumption of germanium was es-
timated to be ca. 70 t of the element in 1986. The
main producers of germanium end products are
located in the United States, Belgium, France,
Federal Republic of Germany, and Japan.
Germanium is considered as a strategic mate-
rial by the United States government. The erec-
tion of a stockpile with a capacity of 30 t of Ge
was decided in 1984. The first delivery began in
1987 and the capacity may be increased to 140 t.
2. Physical Properties
Although high-pressure polymorphs are known,
germanium normally crystallizes in the dia-
mond structure with comparatively weak cova-
lent atomic bonding, yielding the typical hard-
ness and brittleness, as well as the semiconduc-
tor behavior of this gray amphoteric metal.
2 Germanium and Germanium Compounds

The specific structure of the forbidden energy 3. Chemical Properties [2], [3]
gap (band gap E g ), the binding forces between
the germanium atoms, and their mass determine Elemental Germanium. Metallic germa-
the major electron – photon and photon –phonon nium is stable in air. At temperatures above
interactions in the crystal lattice, which result in 400 ◦ C in oxygen, a passivating oxide layer is
a broad optical transmission range for infrared formed. This layer is destroyed by water vapor.
radiation. The fact that this range covers a main Germanium resists concentrated hydrochlo-
atmospheric transmittance window between 7 ric and hydrofluoric acids even at their boiling
and 14 µm, coinciding with the spectral emit- points, but reacts slowly with hot sulfuric acid.
tance peak of a blackbody at room temperature, The dissolution of germanium in nitric acid pro-
has promoted the use of germanium as an in- ceeds faster than in sulfuric acid. In alkaline
frared optical material. Germanium’s high re- media in the presence of an oxidizing agent,
fractive index results not only in high optical e.g., hydrogen peroxide, germanium dissolves
power and little spherical aberration, but also in rapidly, even at room temperature. Germanium
the need for antireflection coatings. These ma- reacts readily with halogens to form tetrahalides.
terials often occur as exotic contaminants in re- Germanium and silicon are totally miscible
cycling operations. Germanium’s thermal prop- and form a continuous range of alloys. The sys-
erties sensitize this brittle material to thermal tem with tin has a eutectic.
shock; crucible design and seeding techniques
must also cope with a 6.6 % volumetric expan-
sion of germanium during solidification. Germanium Compounds. Germanium can
Due to the occurrence of a narrow band gap, have valences of two or four. The divalent com-
most physical properties of germanium (e.g., re- pounds are less stable and oxidize easily to the
sistivity) depend strongly on temperature as well tetravalent compounds, which are similar to their
as on minute concentrations of solutes. An up- silicon analogs.
dated and extensive compilation of the physical Germanium dioxide [1310-53-8], GeO2 Mr
properties of germanium can be found in [1]; Ta- 101.59. Some properties of germanium diox-
ble 1 summarizes typical room temperature val- ide are listed in Table 2. It exists in two crys-
ues. talline forms and one amorphous form, all of
which are white powders. The hexagonal form
is obtained when germanium tetrachloride is hy-
drolyzed with water. This reaction leads to a vo-
Table 1. Physical properties of germanium at room temperature
luminous gel that continuously releases its water
Property Value during drying. The transformation to the tetrag-
onal form occurs only on heating at 300 – 900 ◦ C
Mechanical
Lattice parameter, nm 0.565790 in the presence of a catalyst (e.g., an alkali metal
mp, K 1210.4 halide).
Density, g/cm3 5.3234 The amorphous form is obtained by rapid so-
Microhardness
(Vickers-ASTM E384), kg/mm2 780
lidification of molten GeO2 or by reaction of
Tensile fracture strength, MPa 100 GeCl4 or GeO with oxygen in the gas phase.
Electrooptical Moisture catalyzes the transformation from the
Band gap, eV 0.67 amorphous to the hexagonal form.
Intrinsic resistivity, Ωcm 47.6
Transmission Germanium monoxide [20619-16-3], GeO,
wavelength range, µm 2 – 16 M r 88.59, is obtained by the reaction of GeO2
Absorption coefficient with reducing agents like germanium metal,
at λ = 10.6 µm, cm−1 0.02
iron, carbon, carbon monoxide, or hydrogen
Refractive index
at λ = 10.6 µm 4.0027 above 600 ◦ C. Germanium monoxide sublimes
Thermal above 710 ◦ C, and this property is used in some
Thermal conductivity, W cm−1 K−1 0.586 industrial processes to recover germanium from
Specific heat, J kg−1 K−1 310
Linear thermal expansion, K−1 5.9×10−6
slags or residues (fuming of Ge). Germanium
monoxide is insoluble in water.
 Germanium and Germanium Compounds 3
Table 2. Properties of germanium dioxide

Property Structure

Hexagonal Tetragonal Amorphous

Thermal
stability, ◦ C 1049 – 1116 <1049
Density at 25 ◦ C, g/cm3 4.228 6.239 3.637
mp, ◦ C 1116 1086
Solubility in
water at 25 ◦ C, g/L 4.53 insoluble 5.18
water at 100 ◦ C, g/L 13 insoluble
HF, HCl, NaOH soluble insoluble soluble

Table 3. Properties of germanium tetrahalides

Property GeCl4 [10038-98-9] GeF4 [7783-58-6] GeBr4 [13450-92-5] GeI4 [13450-95-8]

Mr 214.43 148.6 392.26 580.28

Form at 25 ◦ C liquid gas crystals crystals
Color colorless colorless gray white red
Density at 25 ◦ C 1.8755
mp, ◦ C −49.5 −15 26.1 146
bp, ◦ C 83.2 −36.5 (sublimes) 186.5 348

Germanium Halides. Of the germanium GeH4 , digermane [13818-89-8], Ge2 H6 , and

halides, only Germanium tetrachlorgermanium trigermane [14691-44-2], Ge3 H8 , can be sep-
tetrachloride [10038-98-8] has practical appli- arated by fractional distillation.
cations. The properties of the tetravalent halides Organometallic Compounds. The organo-
are listed in Table 3. ide is obtained by reaction metallic compounds of germanium have few
of chlorine gas with germanium metal and of technical uses. Properties and methods of prepa-
hydrochloric acid with GeO2 or germanates. ration have been extensively described [4].
Germanium tetrachloride is soluble in carbon Table 4. Germanium minerals
tetrachloride. Industrial practice takes advan-
Name and composition Ge Mining location
tage of the insolubility of GeCl4 in concentrated content, wt %
HCl (>6M) to purify GeCl4 from trace impuri- Stottite, FeGe(OH)6 29 none
ties such as As, Cu, and B by solvent extraction Schauerteite, 14 none
with HCl. Ca3 Ge(SO4 )2 (OH)6 · 3 H2 O
Briarite, Cu2 (Fe, Zn)GeS4 13 – 17 none
Germanium disulfide [12025-34-2], GeS2 , Germanite, Cu3 (Ge, Fe)S4 5 – 10 Tsumeb, Namibia
M r 136.72, is obtained by the action of H2 S on Renierite, 6.3 – 7.7 Tsumeb, Namibia
acidic germanium solutions. Because GeS2 is (Cu, Fe, Ge, Zn, As)S
insoluble in acid media, this reaction is used in- Kipushi, Zaire
Argyrodite, 4Ag2 S · GeS2 1.8 – 6.9 Freiberg, Germany
dustrially to obtain germanium concentrate. Canfeldite, 0.1 Bolivia
Germanates are obtained in reactions at el- 4Ag2 S · (Sn, Ge)S2
evated temperature (800 – 1200 ◦ C), in which
glasses are produced from melts of GeO2 and
metal oxides or carbonates. The reactions also
occur at room temperature in aqueous so- 4. Resources and Raw Materials [5],
lution; e.g., sodium germanate [12195-31-2], [6]
Na3 HGe7 O16 , is formed by treatment of a
NaOH solution of GeO2 with sulfuric acid. The concentration of germanium in the earth’s
Germanides can be produced by melting crust averages 6.7 ppm, which is comparable to
other metals with germanium and freezing the the concentration of zinc or lead. Thus, germa-
melt, e.g., Mg2 Ge [1310-52-7]. Germanes ( ger- nium is not scarce, but it is widely dispersed so
manium hydrides) are evolved when germanides that only a few minerals have been isolated. The
react with acids: monogermane [7782-65-2], most important are listed in Table 4.
4 Germanium and Germanium Compounds

Germanium is present in the lattices of certain [6873-77-4]), or oxime derivatives (e.g., Kelex
sulfides, such as sphalerite. The concentration of 100 [29171-27-5], and LIX26 [85746-33-4]) [7–
germanium in some germanium-rich deposits is 18]. Fixation of germanium on resin impreg-
given in Table 5. nated with amines has also been patented [19].
However, published information on all of these
Table 5. Germanium content of diverse deposits
is scarce and not always reliable.
Type Location Estimated The second step relies on the volatility of
Ge content, GeCl4 as the separation – purification step. Be-
ppm cause the processes used by the diverse produc-
Zinc ∗ Gordonsville, Tennessee, ers are quite similar, this step can be described
United States 400 with one flow sheet (see Fig. 6).
Nanisivik, Baffin, Canada 230
Saint Salvy, France 150
Tsumeb, Namibia 250
Lyon Lake, Ontario, Canada 200 – 250
Salafosa, Italy 200
Bleiberg, Austria 200
Copper Apex, Utah, United States 640
Coal Northumberland,
United Kingdom 300

∗ Germanium concentration in zinc concentrate.

In the past, germanite (Tsumeb) and renierite

(Kipushi) were the principal sources of germa-
nium. Currently, germanium is recovered mainly
from byproducts of the zinc industry.
The only mining operation specific for ger-
manium (and Ga) is located at an old copper
mine, the Apex, that has been reopened for this
purpose.
At one time, germanium was recovered from
the coal ash of electric power plants in England.
This source of germanium vanished due to the
decreased coal consumption for electric power
production. The former Soviet Union, and prob-
ably China, still recover germanium from this
source.

5. Production
The overall production processes can be divided
into two steps: (1) production of germanium
concentrate (primary production) and (2) pro-
duction of germanium end products.
The first step varies depending on the raw
materials processed and the chosen technology.
Pyrometallurgical processes are based on the
volatility of GeO and GeS. Hydrometallurgic
processes are based on precipitation of germa-
nium as its sulfide or hydroxide or with tannic
acid [1401-55-4].
More recently, solvent extraction has been
reported using hydroxyoximes (e.g., LIX63
Figure 1. Production of a germanium concentrate: flow
sheet of Bleiberger Bergwerks Union (BBU)
Location: Arnoldstein, Austria; Bleiberg mine. Estimated
Ge capacity: 6 t/a.
5.1. Production of Germanium
Concentrate
The flow sheets for the production of germanium
concentrate from germanite and renierite as raw
materials have been described [20].
 Germanium and Germanium Compounds
5.1.1. Bleiberger Bergwerks Union
Bleiberger Bergwerks Union (BBU) processes
the leach residues of its own zinc plant by
a thermic process in a modified Waelz oven
(Fig. 1). Germanium monoxide is sublimed at
ca. 1200 ◦ C. After the fumes are leached,
germanium is precipitated with tannic acid
[1401-55-4]. The germanium-free solution is re-
cycled to the zinc plant and the germanium con-
centrate is sold as such.
The use of tannic acid leads to a relatively
poor germanium concentrate. Care must be
taken to avoid problems in the zinc electroly-
sis due to the recycling of unreacted tannic acid
[21–23].
Figure 2. Production of a germanium concentrate: flow
sheet of Jersey Minière Zinc (JMZ) and Metallurgie
Hoboken-Overpelt (MHO)
Locations: JMZ at Clarksville, Tennessee, United States;
Gordonsville mine. MHO at Olen, Belgium. Estimated Ge
capacity: 65 t/a
5
5.1.2. Jersey Minière Zinc
Jersey Minière Zinc produces zinc from its
mines in Gordonsville and Elmwood, Ten-
nessee. Germanium is concentrated in the leach
residue, which is dried and shipped to Met-
allurgie Hoboken-Overpelt (MHO), Belgium
(Fig. 2) [24].
At the Olen plant in Belgium, the germanium
residue is leached, and germanium is separated
by solvent extraction. After elution in an alka-
line medium, a germanium concentrate is pre-
cipitated by hydrolysis [25]. The use of solvent
extraction technology enables MHO to produce
very rich germanium concentrates, regardless of
the concentration in the feed [8–13].
Figure 3. Production of a germanium concentrate: flow
sheet of Musto Exploration.
Location: St. George, Utah, United States; Apex mine. Ca-
pacity: 18 t/a of Ge and 10 t/a of Ga.
5.1.3. Musto Exploration
The Ge – Ga concentrates from the company-
owned Apex mine are leached in sulfuric acid
with SO2 to reduce trivalent iron (Fig. 3). After
cementation with iron to remove copper, H2 S
is added to give a first sulfide concentrate. Gal-
lium is then separated by solvent extraction. The
6 Germanium and Germanium Compounds
germanium concentrate containing ca. 3 % ger-
manium is upgraded to GeO2 of 98 % purity be-
fore being sold to refiners. Exploitation started
in 1985 [26].
5.1.4. Peñarroya
Concentrates of Zn – Pb and germanium matte
from Pertusola (see Fig. 5) , a subsidiary of
Peñarroya, are processed together by the Impe-
rial Smelting Process. Germanium is collected
in the zinc phase, which is further purified by
distillation in New Jersey columns (Fig. 4). Ger-
manium is then concentrated in a residue by
volatilization of zinc. However, due to ecologi-
cal problems, thermal processes for zinc are los-
ing importance compared with hydrometallurgic
processes.
Figure 4. Production of a germanium concentrate: flow
sheet of Peñarroya
Location: Noyelles-Godault, France; Saint-Salvy mine. Ca-
pacity: GeO2 – GeCl4 , 60 t/a; Ge metal, 30 t/a
5.1.5. Pertusola
The zinc concentrates of Salafosa are treated
at the refinery of Crotone (Fig. 5). The leach
and purification residues of the hydrometallur-
gic plant are thermally decomposed in a cubilot.
Germanium is recovered in the Pb – Zn fumes, a
small portion going into the matte phase, which
is processed further by Peñarroya (Fig. 4). After
releaching the fumes, a germanium concentrate
containing 7 – 35 % germanium is produced.
Figure 5. Production of a germanium concentrate: flow
sheet of Pertusola
Location: Crotone, Italy; Salafosa mine.
5.1.6. Other Primary Producers
The Metallgesellschaft (Germany) recovers ca.
10 t/a of germanium from the hydrometallur-
gical plant of Datteln. China exports ca. 4 t/a
of germanium. The production of the former
Soviet Union is mainly used internally (esti-
mated 40 t/a of germanium). Cominco (British
Columbia, Canada) is developing a project for
10 – 20 t/a of germanium.
Eagle Picher (Quapaw, Oklahoma, United
States) processed the residues of its zinc smelter
by fuming in a Waelz oven at 1250 ◦ C. Be-
 Germanium and Germanium Compounds
cause this source is not economical at cur-
rent prices, Eagle Picher now supplies its re-
fining unit (25 – 40 t/a of germanium capacity)
with purchased germanium concentrates [27].
Preussag (15 t/a) and Otavi (5 t/a) (both Fed-
eral Republic of Germany) processed german-
ite from Tsumeb before depletion, but they now
buy concentrate [5].
Figure 6. Flow sheet of the production of germanium metal
from germanium concentrate
5.2. Production of Germanium from
Germanium Concentrate
The transformation of a germanium concentrate
(mostly GeO2 ) or germanium metal scrap to ger-
7
manium (Fig. 6) [28] begins with conversion to
GeCl4 :
GeO2 + 4 HCl → GeCl4 + 2 H2 O
Ge + 2 Cl2 → GeCl4
The reactions are run at the boiling point of
GeCl4 (83.2 ◦ C) in concentrated HCl (6 M) to
avoid hydrolysis. Even when only GeO2 is pro-
cessed, a chlorine atmosphere is used to oxidize
the volatile AsCl3 to nonvolatile H3 AsO4 .
The GeCl4 , containing As3+ as the major
impurity, is purified by fractional distillation.
Traces of As, Sb, Cu, and B are extracted by
HCl (>6 M) saturated with chlorine. Other pu-
rification techniques have been reviewed [20].
The purified GeCl4 is hydrolyzed with high-
purity water,
GeCl4 + 2 H2 O → GeO2 + 4 HCl
After filtration and thorough washing, the GeO2
is dried.
The usual method of producing elemental
germanium is hydrogen reduction [29] of ger-
manium dioxide in electrically heated tubular
furnaces at ca. 650 ◦ C, yielding a gray metallic
germanium sponge. In industry, graphite and/or
quartz boats and furnace linings are used. Quartz
boats must be sandblasted and/or coated to avoid
sticking and breakage.
Care must be taken to keep the temperature
below 700 ◦ C during reduction to avoid genera-
tion of volatile germanium monoxide. Adequate
processing limits the germanium loss to less than
0.1 wt %.
As a result of the very stringent purity re-
quirements, reduction processes [2] using car-
bon, flux electrolysis, or the direct reaction of
germanium tetrachloride with zinc have lost in-
dustrial importance. The reaction of GeCl4 with
H2 can be used to grow epitaxial germanium
layers [30], but bulk germanium production is
hampered by low metal yield and overall energy
yield.
After complete reduction, the temperature is
raised above the melting point (937 ◦ C), and a
polycrystalline germanium bar is solidified from
one end to the other. Due to the different solu-
bilities of the impurities in the liquid and solid
8 Germanium and Germanium Compounds
phases, the impurities concentrate by segrega-
tion [31] in the first or the last melt fraction to so-
lidify. Hydrogen is highly soluble in molten ger-
manium; therefore, to avoid porosity and blow
holes, the crystallization speed must be limited
to a few centimeters per hour.
5.3. Purification
To obtain semiconductor-grade germanium, the
material must be further purified by zone re-
fining [32], [33], under hydrogen, nitrogen, or
another controlled atmosphere. Due to the low
surface tension and high density of molten ger-
manium, a crucible-free float zone-refining pro-
cess never matured [34] (→ Crystal Growth,
Chap. 6.4.). High-purity germanium is ob-
tained by repeated passage of crude germanium
through the zone-refining crucible. The number
of efficient zone-refining passes which can be
carried out in a single crucible is limited by the
partition coefficient of the impurities between
germanium and the crucible material. Eventu-
ally, an equilibrium between the concentration
of impurities in the melt and in the crucible
is reached. For this reason, a cyclic batch pro-
cess, in which the zone refining is continued
in a new crucible, is unavoidable if high-purity
germanium is to be obtained. Between the suc-
cessive refining steps, the less pure metal parts
are mechanically cut away and recycled. A suit-
able etching technique [35] is required to clean
and prepare the load as well as the crucible
for the next refining step. Grain boundaries and
other crystallographic imperfections (disloca-
tions, vacancies, etc.) act as precipitation sites
for impurities, impeding the ultrapurification.
Ultimate purity levels can therefore be ob-
tained (and measured) only in single crystals
grown in the most aseptic, dust-free environ-
ment. The physics and chemistry of ultrapurifi-
cation of germanium have been discussed [36–
38].
5.4. Transformation Processes
For most applications, the germanium must be
processed further into a suitable size and crystal-
lographic perfection and doped within a narrow
range (e.g., 1– 8 ppb) with a definite impurity
(usually a group 13 or group 15 element) to yield
the specified electrooptical properties.
Two techniques are available for this trans-
formation: (1) the Bridgman process [39] which
entails horizontal or vertical, possibly seeded,
directional solidification in a graphite crucible,
often improperly called casting, and (2) the
Czochralski process [40], by which a crystal
seed is dipped into a germanium melt and al-
lowed to grow by suitable control of pull speed
and heat balance (→ Crystal Growth, Chap. 6.).
The second process yields the most perfect
material, e.g., dislocation-free single crystals.
The fundamental physicochemical background
of crystal-growth processes was reviewed [41–
43]. Modern equipment handles up to 150 kg
germanium loads and allows growth of single
crystals up to 300 mm in diameter in a typical
48 h cycle.
Germanium crystals are ground, sliced, and
milled with high precision microcomputer-
controlled, diamond-tooled machines into the
desired geometrical shape. This operation gen-
erates huge and costly amounts of scrap fines
which have to be recycled. The brittleness of ger-
manium and the need to preserve a near-perfect,
strain-free crystal lattice do not allow germa-
nium forging; segregation of the indispensable
dopants hinders precision casting.
6. Environmental Protection
In the primary production of germanium, envi-
ronmental problems are not specific to germa-
nium, but are those of the zinc industry (e.g.,
SO2 emission, cadmium pollution).
When solvent extraction units are used (see
Section 5.1), special attention must be paid to
fire protection and cleaning of the off-gas. The
off-gas of GeCl4 production must be scrubbed
with alkaline solution to destroy HCl and chlo-
rine. Monitoring the hydrogen content in the air
avoids any risk of explosion in the reduction sec-
tion.
7. Quality Specifications
Major impurities (<10 ppm) in GeCl4 are O, C,
and H, all detectable by infrared spectrometry.
 Germanium and Germanium Compounds
The concentration of all metallic impurities can
be depressed to or below their detection limits
(typically <5 ppb). Process-induced impurities
in GeO2 are H2 O (<3000 ppm, ASTM F5-60)
and Cl (<300 ppm, turbidimetry). Often, C, F,
and S are detected at ppm levels (conductime-
try); all other elements are at or below their de-
tection limit (<10 ppb).
Density (ASTM B 417-76, B 527-70) and
grain size (ASTM B 330-76) obviously influ-
ence reduction kinetics, but the contamination
risks inherent to all high-temperature processes
suggest the use of all-quartz furnaces and syn-
thetic quartz boats with palladium-diffused H2
for the assessment of electronic grade GeO2 by
reduction (ASTM F 27-83).
The most commonly used characterization
techniques for germanium metal are those that
determine the electrical properties of semicon-
ductors: e.g., transport properties (ASTM F 43-
78, F 76-73, F 42-77) and crystallographic per-
fection (ASTM F 389-76). For evaluation of the
optical quality of germanium, a number of rou-
tine spectroscopic and specialized interferomet-
ric techniques exist [44]. All of these methods
are, however, sensitive to the surface preparation
(polishing) of the sample. Since many of the op-
tical and electronic properties of germanium are
linked to one another [45], [46], the electronic
properties, which can be more accurately and re-
liably measured, can be used to define the optical
properties. Thus, for example, standard optical
grade germanium is specified as n-type germa-
nium with resistivity 5 – 40 Ωcm.
To determine the chemical nature and con-
centration of electrically active impurities, three
sensitive (10−5 ppb) techniques are used: deep
level transient spectroscopy (DLTS) [47], far
infrared transmission (FIRT) [48] (Fig. 7), and
photothermal ionization spectroscopy (PTIS)
[49].
Impurity, “As reduced” Refined
ppb
P 1.5 0.36
As 0.77 0.005
Al 1.1 0.27
Ga 0.031 0.005
The major residual impurities in high pu-
rity germanium (H2 < 100 ppb; C, Si, and
O < 10 ppb) are process-induced and barely de-
tectable by their lattice phonon absorption in the
9
germanium matrix (ASTM F 120-75, F 122-74)
or by autoradiospectrometry [50], [51]. The con-
centration of other impurities can be depressed
below 10−3 ppb.
Figure 7. Purification by zone refining
a) 8K-FIRT spectra of germanium “as reduced” vs. b) after
zone refining
8. Chemical Analysis
The analytical determination of germanium has
been reviewed [52].
Germanium can be determined by pho-
tometry at 510 nm after complexation with
phenylfluorone [975-17-7]. Atomic absorption
spectroscopy at 261.1 nm is less sensitive than
the previous method. X-Ray fluorescence en-
ables determination down to 5×10−3 %. Po-
larographic methods such as differential pulse
polarography and anodic stripping have been
developed for the determination of germanium
(and other impurities) in Zn electrolytes.
The determination of impurities in GeCl4 ,
GeO2 , and Ge can be achieved by graphite fur-
nace atomic absorption spectroscopy (GFAAS)
[53] or spark source mass spectroscopy [54].
9. Storage and Transportation
Germanium tetrachloride is classified as a
dangerous corrosive liquid subject to interna-
tional regulations (ADR/RID-IMDG-IATA) un-
der UN 1760 Class 8 Group II. The combina-
tion of these with the very stringent purity re-
quirements of the optical fiber manufacturers
demands the use of expensive packaging (e.g.,
glass/teflon [9002-84-0], tantalum-coated steel
[7440-25-7]).
10 Germanium and Germanium Compounds
Table 6. Germanium market in 1986 ∗
Application Product
Infrared optics optical-grade Ge,
shaped mono- and poly-
crystalline blanks
Optical fibers high-purity GeCl4
Catalysis GeO2 (hexagonal or
amorphous), NaH3 Ge2 O6
Electronics, optoelectronics doped Ge single-crystal slices
High-energy radiation detectors high-purity Ge single crystal
Luminescence GeO2
Medical, alloys, and glasses GeO2 , Ge pellets, and powders
Total
∗ Excluding Eastern-bloc countries
The packaging should preserve the purity of
the GeO2 during transportation and storage. For
relatively short storage, a hermetically sealed
high-density polyethylene bottle is satisfactory.
The quality degradation during longer storage is
linked to diffusion of impurities through or dete-
rioration of the polyethylene. In this case the use
of fluorinated plastic foil or coating is advisable.
Germanium metal oxidizes slowly in air;
therefore, its packaging should primarily take
its brittleness into account.
10. Uses and Economic Aspects
Germanium is used in manufacturing a wide
range of high-technology products. Table 6
summarizes these applications for the market
economies with respect to market volume and
trends, as well as the germanium compound
used.
The use of germanium in optical materials,
by far the most important today, represents ca.
50 % of the world consumption. Germanium it-
self is the primary high-quality lens and window
material for thermal imaging in the 8 – 12 µm
wavelength range. The materials trade-off for
this application was reviewed [55]. The replace-
ment of silicon by germanium as a cation in op-
tical glasses [56] extends their transmittance to-
ward longer wavelengths and increases the re-
fractive index. The second property is used to
confine the signal within the core of telecom-
munication optical fibers. The chemistry of ger-
manium in fiber manufacture is discussed in
[57]. With As, Sb, and Se, germanium forms
Consumption, t Annual growth rate, %
35 15
13 10
13 5
2 5
1 5
1
5 5
70 11
nonoxide glasses [58], also used in IR optics
(Fig. 8), and whose photosensitivity yields high-
resolution photoresists [59].
Figure 8. Germanium for infrared optics: typical set of pol-
ished Ge blanks
The second major use of germanium is as cat-
alyst or cocatalyst [60] in the production of poly-
esters (e.g., poly(ethylene terephthalate)) and
synthetic textile fibers. The more expensive ger-
manium catalysts are used when the final prod-
uct must be a colorless fiber or plastic, e.g., pho-
tographic films.
Some germanates crystallize as typical
phosphors, which reemit absorbed energy
as visible radiation. Magnesium germanates
and fluorogermanates, e.g., Mg28 Ge10 O48 and
Mg56 Ge15 O66 F20 , in which magnesium acts as
activator, are used in lamps as a constituent
of the fluorescent coating [61]. This is pre-
ferred to the cheaper arsenic-based phosphors,
for which safety regulations are severe. Bismuth
germanate [12233-56-6], Bi4 Ge3 O12 , is an in-
 Germanium and Germanium Compounds
trinsic phosphor that is used as a single crystal
in high-energy gamma-ray scintillator detectors
[62]. The stopping power is extremely high be-
cause of the high atomic number of bismuth.
The remaining interest for germanium in
electronics is based on the advantageous mobil-
ity characteristics of charge carriers in this ma-
terial. Typical applications are high-power de-
vices with low energy loss and photodetectors
[63]. The most demanding photodetector appli-
cation involves gamma-ray spectroscopy detec-
tors [64], for which germanium must be refined
to an extremely low impurity level (<10−3 ppb)
and grown in nearly perfect single crystals. Re-
cent progress in producing stable insulating lay-
ers on germanium [65], as well as its crys-
tal lattice match (∆a/a < 5×10−3 ) with GaAs
[1303-00-0] (epitaxy) offers new hope for ger-
manium as an electronic material in integrated
circuits.
Figure 9. Belgian producer price for electronic-grade ger-
manium dioxide (June 30 values from Metal Bulletin; the
Belgian franc is the usual currency for the quotation of
GeO2 )
Another use of germanium, although lim-
ited virtually to Japan, is the industrial pro-
duction of organogermanium compounds such
as bis(carbamoylethylgermanium) sesquiox-
ide [27031-32-9], (GeCH2 CH2 CONH2 )2 O3 ,
for medical applications [66]. The use
of germanium in alloys, e.g., high-
precision resistors, is minor. The geographic
production – consumption pattern for 1986 is
summarized in Table 7.
11
Table 7. Production – consumption pattern for Ge in 1986
Country Production, t Consumption, t
North America 29 35
Western Europe 36 18
Asia 5 17
In consideration of the large internal scrap re-
cycling coefficient of most production lines (see
Section 5.2), care should be taken in evaluating
the apparent refining overcapacity of many pro-
ducers.
Figure 9 illustrates the producer price evo-
lution of electronic-grade GeO2 , largely deter-
mined by the refining costs of low-grade ores.
The price of germanium metal in its various
commercialized forms reflects the stringent re-
quirements for purity and crystallographic per-
fection and, therefore, depends strongly on the
specifications.
11. Toxicology and Occupational
Health
Germanium and most germanium compounds
are comparatively low in toxicity because
of pharmacological inertness, diffusibility, and
rapid excretion. However, some exceptions ex-
ist, the most important being germanium hy-
dride (germane). Surprisingly, soluble germa-
nium compounds are more toxic by oral than
by parenteral uptake. Intoxication is character-
ized by a lack of gross tissue changes in animals
dying from oral uptake of germanium. Industrial
exposure is due mainly to germanium fumes and
dusts generated during production.
Absorption, Metabolism, Excretion, and
General Effects. Gastrointestinal absorption of
germanium oxides and cationic salts is poor;
in contrast, the absorption of germanates from
small oral doses is ca. 75 % in 4 h and 96 % in 8 h
[67]. Inhaled germanates are quickly absorbed
from the lungs into the blood [68]. Elemental
germanium and germanium dioxide are excreted
mainly via the urine in rats, rabbits, and dogs
[69]. No reports of Ge accumulation in human
or animal tissues exist. High exposure levels of
germanium salts disturb water balance leading
to dehydration, hemoconcentration, decrease in
blood pressure, and hypothermia [70], without
showing gross tissue damage.
12 Germanium and Germanium Compounds
Acute Toxicity. The symptoms of acute ger-
manium toxicity in animals are listlessness,
marked hypothermia, diarrhea, cyanosis, edema,
hemorrhage of the lungs, petechial hemorrhage
in the wall of the small intestine, peritoneal ef-
flusion, and edematous changes in heart muscle
and in parenchymal cells of the liver and kid-
neys [71]. Germanium tetrafluoride and tetra-
chloride vapors irritate the eyes and mucous
membranes of the respiratory tract [72]. Organic
compounds, such as dimethylgermanium oxide
[1112-60-3], are only slightly toxic to rats [73],
whereas triethylgermanium acetate [5061-27-8]
shows considerable toxicity [74]. Germanium
metal dust (particle size 1.7 µm, concentration
unknown) and GeO2 (particle size 0.45 µm, con-
centration unknown) had no adverse effects on
rats after inhalation for 1 h [68]. In rats and mice,
the acute oral toxicity of alkylgermanium com-
pounds ranged between 300 and 2870 mg/kg
[74], [75]. Triethylgermanium acetate has an
LD50 value (rat, oral) of 250 mg/kg body weight.
The LD100 for germane (mouse, inhalation) is
610 mg/m3 [67].
Germanium hydride, GeH4 , is a colorless,
highly inflammable, toxic gas of low stability
with a characteristic unpleasant odor. By inhala-
tion, gaseous germanium hydride is the most
toxic of germanium compounds. Inhalation of
GeH4 (70 mg/m3 , minimally effective concen-
tration) for 2 – 15 d caused nonspecific and non-
persistent changes in the nervous system, kid-
neys, and blood composition. Like other metal
hydrides such as AsH3 , it shows hemolytic ac-
tion in animals [76]. The lethal concentration in
air is 150 ppm [77].
Chronic Toxicity. Symptoms of chronic ger-
manium intoxication in experimental animals
are mainly fatty degeneration of the liver and in-
hibition of growth: 1000 ppm neutralized GeO2
(pH adjusted to 7) given in the diet of rats for 14
weeks depressed growth and caused 50 % mor-
tality; 5 ppm germanium administered as ger-
manates in the drinking water of rats and mice
resulted in decreased life-span and mild fatty de-
generation of the liver; 100 ppm GeO2 in the
drinking water for 4 weeks caused 50 % mortal-
ity without hematological or gross pathological
changes.
Exposure Limits. A TLV for germane of
0.2 ppm, equivalent to 0.64 mg/m3 , was fixed
by the TLV Committee of the American Con-
ference of Governmental Industrial Hygienists
in 1973 as an average limit of permissible expo-
sure during an 8-h working day. No other TLVs
for germanium or its compounds have been set
in industrialized countries. Neither germanium
nor its compounds are considered or suspected
to exert a carcinogenic effect on humans or ani-
mals [78].
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6. U.S.B.M., Minerals Yearbooks, U.S. Dept. of
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 Germanium and Germanium Compounds
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28. J. E. Hoffmann, J. Met. 6 (1987) 42 – 45.
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(Jpn.) 20 (1978) no. 2, 111 – 127.
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no. 1, 81 – 87.
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Semiconductors by Crystallisation, Freund
Publ. House, Tel Aviv 1971.
32. W. G. Pfann: Zone Melting, J. Wiley & Sons,
New York 1958.
33. K. Hein, E. Buhrig: Kristallisation aus
Schmelzen, VEB Deutscher Verlag für
Grundstoffindustrie, Leipzig 1983.
34. A. F. Bogenschütz: Aetzpraxis für Halbleiter,
Hauser Verlag, München 1967.
35. P. J. Holmes: The Electrochemistry of
Semiconductors, Academic Press, London
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36. E. E. Haller, W. L. Hansen, F. S. Goulding,
Adv. Phys. 30 (1981) no. 1, 93 – 138.
37. L. S. Darken, J. Electrochem. Soc. 126 (1979)
no. 5, 827 – 833.
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(1979) no. 1, 324 – 333.
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(1925) 305.
40. J. Czochralski, Z. Phys. Chem. 92 (1917)
219 – 221.
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Growth, (Solid State Science no. 5) Springer
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42. J. C. Brice: Crystal Growth Processes,
Blackie, Glasgow 1986.
43. A. A. Chernov, Modern Crystallography III,
Crystal Growth (Solid State Science no. 36)
Springer Verlag, Berlin 1984.
44. J. A. Savage, Proc. SPIE Int. Soc. Opt. Eng.
274 (1981) 175 – 179.
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Appl. Opt. 21 (1982) no. 8, 1490 – 1495.
46. L. Van Goethem, L. P. Van Maele, M. Van
Sande, Proc. SPIE Int. Soc. Opt. Eng. 683
(1986) 160 – 165.
13
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18 (1985) 2041 – 2058.
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Goethem, Proc. Int. Conf. Shallow Impurity
Centers, 2nd, Triest (1986).
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Condens. Matter 33 (1986) no. 12, 8180.
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Jarrel, IEEE Trans. Nucl. Sci. NS 29 (1982)
no. 1, 738 – 744.
51. W. Hansen, E. Haller, P. Luke, IEEE Trans.
Nucl. Sci. NS 29 (1982) no. 1, 745 – 750.
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Morrison, Y. Karpov, Pure Appl. Chem. 57
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54. C. Verlinden, R. Gybels, F. Adams, J. Anal.
Atom. Spectr. 1 (1986) 411 – 419.
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Their Antireflection Coatings, Adam Hilger,
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J. R. Simpson, R. Csencsits, J. Lightwave
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Cliffs, N.J., 1971.
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Integrated Circuit Fabrication and Technology
(Am. Chem. Soc.) 1984.
66. K. Asai: Organic Germanium, A Medical
Godsend, Kogakusha, Tokyo 1977.
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in Mammals,” Chemical Toxicity of Metals and
Metalloids, vol. 2, Plenum Press, New
York-London 1978.
14 Germanium and Germanium Compounds
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Ghatti Gum → Polysaccharides
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Gin → Spirits
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 Glass Ceramics 1

Glass Ceramics
Bernard H. W. S. De Jong, Corning Research, Corning, New York 14831, United States
Jane W. Adams, Corning Research, Corning, New York 14831, United States
Bruce G. Aitken, Corning Research, Corning, New York 14831, United States
James E. Dickinson, Corning Research, Corning, New York 14831, United States
Gerald J. Fine, Corning Research, Corning, New York 14831, United States

1. Introduction . . . . . . . . . . . . . . . 1 3.2.2. Transparency . . . . . . . . . . . . .. . 9

2. Nucleation and Crystallization of 3.2.3. Electrical Properties . . . . . . . . .. . 9
Glass Ceramics . . . . . . . . . . . . . 2 3.2.4. Mechanical Properties . . . . . . . .. . 10
2.1. Homogeneous Nucleation . . . . . . . 2 3.2.5. Durability . . . . . . . . . . . . . . .. . 11
2.2. Heterogeneous Nucleation . . . . . . 3 3.3. Microstructure . . . . . . . . . . . .. . 11
2.3. Crystal Growth . . . . . . . . . . . . . 4
4. Types of Glass Ceramics . . . . .. . 12
2.4. Heat Treatment . . . . . . . . . . . . . 5
4.1. Silicate-Based Glass Ceramics .. . 12
3. Nature of Crystalline Phases . . . . . 6
3.1. Metastability . . . . . . . . . . . . . . . 6 4.2. Aluminosilicate Glass Ceramics . . 14
3.2. Physical Properties . . . . . . . . . . . 7 4.3. Fluorosilicate Glass Ceramics . .. . 16
3.2.1. Thermal Properties . . . . . . . . . . . . 7 5. References . . . . . . . . . . . . . . .. . 17

1. Introduction Literature on glass ceramics is not as exten-

The development of glass ceramics is a compar-
atively recent advance in materials science. The
phenomenal growth in a wide variety of applica-
tions for these materials since their discovery by
Stookey in the late 1950s attests to their great
utility.
Glasses are formed when molten materials
are cooled and form a solid without crystal-
lization (→Glass). Glass ceramics, however, are
uniformly grained, crystalline materials which
are made by controlled nucleation and crystal-
lization of homogeneous glasses. Crystallization
is induced by a nucleating agent and heat treat-
ment. The major advantage of glass ceramics
over conventional ceramics is that fully densi-
fied bodies with complex shapes can be manu-
factured using standard hot glass forming tech-
niques. Glass ceramics also offer a variety of
unique, uniform physical properties, including
great strength, machinability, transparency, and
thermal shock resistance that cannot be attained
in either glass or conventional ceramics.
sive as that for glasses. The excellent recent re-
views of Beall and coworkers [1–4] and Smith
[5] together with the books written by Vogel [6]
and Strnad [7] and the one edited by Lewis [8]
give a proper overview of glass ceramic technol-
ogy.
2. Nucleation and Crystallization of
Glass Ceramics
The specific properties of glass ceramics are
controlled by the physical properties of the crys-
talline phases developed in the glass upon heat
treatment and also by their microstructure, i.e.,
the textural relationship between the crystalline
phases and the residual glass. The uniformity
and reliability of these properties is a conse-
quence of the uniform grain size of the crys-
talline phases. Therefore, an important prereq-
uisite for the formation of glass ceramics is ef-
ficient nucleation of the crystalline phases. The
heat treatment (ceramming) of glasses to pro-
duce a glass ceramic typically involves two or

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 433
2 Glass Ceramics
more steps: a lower temperature step to induce
nucleation (the nucleation hold), and one or
more higher temperature treatments to promote
crystal growth (crystallization hold).
2.1. Homogeneous Nucleation
Homogeneous nucleation occurs when crystals
are formed within a supersaturated fluid without
addition of foreign particles. The parameters in-
volved in crystal nucleation are shown in Equa-
tion (1) which expresses the steady-state homo-
geneous nucleation rate in a one-component su-
percooled system [8], [9]:
I =Aexp [− (W +∆GD ) /kT ]
Here I is the number of nuclei formed per unit
volume, W is the free energy barrier to forma-
tion of a nucleus of critical size, ∆ G D the kinetic
barrier to nucleation, k is Boltzmann’s constant,
and T is absolute temperature. The preexponen-
tial factor A can be expressed to a first approxi-
mation by
A=nv (kT /h)
where nv is the number of formula units of the
nucleating phase per unit volume of liquid and
h is Planck’s constant.
The parameter ∆ G D is usually expressed as
the activation energy of diffusion in the Arrhe-
nius equation
D=D0 exp (−∆GD /kT )
where D0 = kTλ2 /h, λ being the jump distance
of the atoms in the direction of diffusion. As-
suming validity of the Stokes – Einstein rela-
tion, D can be expressed in terms of the viscos-
ity η as D = kT /6 πλη. Thus exp (−∆ G D /kT ) =
h/6 πλ3 η, and Equation (1) becomes
I = (Ac T /η) exp (−W/kT )
where Ac is nv k/6πλ3 . The free energy barrier
to formation of a critical spherical nucleus W is
W = 16πσ 3 V 2m /3∆G2
where σ is the interfacial energy per unit area
between crystal and liquid, V m the molar vol-
ume of the crystalline phase, and ∆G the change
in free energy per mole of material crystallized.
Substitution into Equation (4) gives the final ex-
pression for the steady-state homogeneous nu-
cleation rate as


I = (Ac T /η) exp −16πσ 3 V 2m /3∆G2 kT (6)
in which time does not appear explicitly be-
cause I does not vary with time in steady-state
homogeneous nucleation.
Although exact evaluation of Equation (6) is
not possible due to the lack of relevant thermo-
dynamic data, interfacial energy values, and nv
data, this equation is still a useful guide for mak-
ing adjustments to produce an efficiently nucle-
ated glass ceramic. For example, it indicates that
(1) lowering the interfacial energy σ should have
the largest effect on increasing nucleation effi-
ciency. This might be accomplished by slight
variations in glass composition, in particular by
addition of WO3 and MoO3 , which effectively
reduce surface tension.
Similarly the number of nuclei per unit vol-
ume I will be larger if the change in free en-
ergy between liquid and crystalline precipitate
is large. Although this free energy change is
(2) largely beyond experimental control, introduc-
tion of components which preferentially enter
into solid solution with the crystalline phase may
lower its free energy relative to the liquid and
hence increase the number of nuclei.
Inspection of Equation (6) also suggests that
increasing viscosity will decrease the nucleation
efficiency because of impeded transport of nu-
(3)
trients to the nucleus. Lowering the viscosity at
the optimal nucleation temperature is therefore
desirable, although this is limited because the
article may sag during the nucleation hold.
The least understood parameter in Equation
(6) is nv , the number of formula units of the nu-
cleating phase per unit volume. The reason for
this is a general lack of understanding of the
relationship between glass and crystalline struc-
(4) ture. Intuition suggests that structural similarity
between the glass and the crystalline structure
would accelerate nucleation because of the in-
creased probability of forming a critical nucleus,
hence increasing nv .
(5)
An expression for the time-dependent nucle-
ation rate I
is given by Kaschiev [10]:


I
=I 1 + 2Σ (−1)m exp −m2 t/τ (7)

where the summation over the index m is from
one to infinity, τ = 48σλ5 η/πV 2 ∆G2v is the in-
duction time, I is the steady-state nucleation rate,
and t is time.
Figure 1. A two-dimensional slice through three-
dimensional Voronoi cells calculated for a random distri-
bution of nucleation sites separated by an average distance
of 32 µm (A, 40 points) and 16 µm (B, 400 points)
Courtesy of Leslie Button (Corning Incorporated).
2.2. Heterogeneous Nucleation
Homogeneous nucleation occurs in only a
small number of glass systems, such as Li2 O ·
Glass Ceramics 3
2 SiO2 , Na2 O · 2 CaO · 3 SiO2 , BaO · 2 SiO2 ,
and SiO2 · P2 O5 . No industrially important glass
ceramic systems nucleate homogeneously. In
most glass ceramic systems, nucleation is het-
erogeneous, i.e., it is a consequence of epitaxial
growth of the dominant crystalline phase upon
nuclei of a foreign or earlier formed phase. The
latter are usually crystallites of relatively refrac-
tory and/or insoluble phases (e.g., rutile, anatase,
ZrO2 , ZrTiO4 , Cr2 O3 , and many of the noble
metals), but can also be globules of an immisci-
ble glass. As a result, “nucleating agents” or “nu-
cleants” such as TiO2 , ZrO2 , P2 O5 , Pt, Pd, and
Au are essential components in the bulk compo-
sition of most commercial glass ceramics. The
nucleation and growth of the nucleating agent
itself can be considered to be homogeneous.
The equation describing the steady-state het-
erogeneous nucleation process is analogous to
that describing homogeneous nucleation:
I ∗ =ns (kT /η) exp [− (W ∗ +∆GD ) /kT ] (8)
In this equation W ∗ is a function of the contact
angle between the nucleating agent (substrate)
and the epitaxial phase, and ns is the number of
formula units per unit volume (i.e., number den-
sity) of the latter in contact with the substrate.
The contact angle is assumed to be a function
of the degree of lattice mismatch between sub-
strate and epitaxial phase. The effectiveness of
heterogeneous nucleation therefore depends on
the structural relationship between the substrate
and the epitaxial phase and on the number den-
sity of heterogeneous nuclei in the supercooled
liquid. The lattice constants of the nucleating
agent and the desired crystalline phase should
agree to within ca. 15 %. Examples are given in
Table 1.
The number density of heterogeneous nuclei
depends strongly on solubility; effective nucle-
ating agents have low solubilities at the nucle-
ation temperature. For any crystalline phase, sol-
ubility is controlled by the interactions among
the melt components. Using TiO2 and ZrO2 as
examples, their relative efficacy as nucleating
agents is partly governed by the relative stabil-
ity of titanate versus zirconate melt complexes.
In alkali silicate glasses TiO2 is not an effective
nucleating agent because it forms stable melt
complexes with alkali-metal ions; ZrO2 , on the
other hand, is more effective because complex
formation is not favored to the same degree [11].
4 Glass Ceramics
Table 1. Lattice constants of crystalline phases used in glass ceramics and their mismatch relative to rutile (TiO2 nucleant)

Crystalline phase Lattice constant, Deviations

nm from TiO2 ∗

a b c

Rutile (TiO2 , nucleant) 0.46 0.30

β-Spodumene (LiAlSi2 O6 ) 0.95 0.83 0.52 a: 3.7 % (2 ar )
b: −9.4 % (2 ar )
c: −11.2 % (2 cr )
β-Eucryptite (LiAlSiO4 ) 0.52 1.12 a: 12.6 % (2 ar )
c: −5.3 % (4 cr )
Cordierite [Mg2 Al3 (AlSi5 O18 ] 1.70 0.98 0.93 a: −6.7 % (4 ar )
b: 6.8 % (2 ar )
c: 1.9 % (2 ar )

∗ Deviations are expressed as percentages relative to the quantity defined in parentheses. The subscript r denotes rutile.

The effect of the number density of hetero-
geneous nuclei on the grain size and, hence, the
texture of a glass ceramic is illustrated in Fig-
ure 1 with the aid of three-dimensional Voronoi
cells. Voronoi cells are geometric constructions
in which polyhedral elements are calculated bet-
ween a set of points such that the distance to each
point is halved. In Figure 1, two cross sections
of three-dimensional Voronoi cells have been
calculated, the one with small crystallites repre-
sented by 400 points, the other with large crys-
tallites represented by 40 points. As illustrated
in Figure 2, a small number of nucleation sites
results in large crystallites (A), a large number
in small crystallites (B).
2.3. Crystal Growth
Once the critical radius of a crystallite is ex-
ceeded, the free energy of the system is lowered
by further crystal growth rather than by crystal
dissolution (Fig. 3). In both homogeneously and
heterogeneously nucleating systems, the critical
radius can be defined as
rc = −2σV /∆G
where V is the volume of the critical nucleus and
σ is the surface free energy. The effect of the nu-
cleating agent on the critical radius in a heteroge-
neously nucleating system is expressed through
the surface energy term; this will be smaller the
greater the structural congruence between the
nucleating agent and the crystalline phase. The
rate of crystal growth ζ is governed by parame-
ters similar to those involved in nucleation. An
equation has been derived by Jackson [13] to
describe continuous growth by random attach-
ment of atoms to surface sites:
ζ =λν (H∆T /kTm T )
·exp (−Qf /kT ) exp (−H/kTm ) (10)
The rate of crystal growth depends on the
thermodynamic driving force H (the enthalpy
of fusion), the jump distance λ, the vibrational
frequency ν, the atomic mobility as expressed by
an activation energy for diffusion Qf , and ∆ T ,
the temperature difference between the melting
temperature T m and the growth temperature T .
As with nucleation, the mobility term can be
expressed in terms of diffusivity and viscosity
by the Stokes – Einstein relation. Equation (10)
then becomes
ζ =hν/6πλ2 η (H∆T /kTm T ) exp (−H/kTm ) (11)
2.4. Heat Treatment
(9)
Although the parameters governing Equations
(8) and (11) are similar, the functional depen-
dence of the nucleation rate and the growth rate
on these parameters is not. Consequently, nucle-
ation and growth rates generally attain maxima
in separate temperature regimes (Fig. 4). As a
result, heat treatment (ceramming) of a glass ar-
ticle to form a glass ceramic typically includes at
least two steps. The first of these is the nucleation
hold: a soak or gradual heating at relatively low

temperature, usually about 50 –100 ◦ C above the
annealing point of the glass. Following the nu-
cleation hold, the temperature is raised rapidly
to that of the crystallization step. The article is
then heated at constant temperature until crystal
growth is complete and the desired microstruc-
ture attained. This is termed the crystallization
hold., Chap. 3.
Figure 2. Calculated distributions for the volume (A) and
surface area (B) of the Voronoi cells illustrated in Figure 1
Each figure shows a narrow distribution (a) with sites sep-
arated by an average distance of 16 µm and a broad distri-
bution (b) with sites separated by an average distance of
32 µm. The areas under the two volume distributions are
normalized with respect to one another. The distributions
of the surface areas calculated from these volume distribu-
tions are therefore not normalized.Courtesy of Leslie Button
(Corning Incorporated).
Glass Ceramics 5
Figure 3. Calculated free energy of formation of a spherical
crystallite of Mg2 SiO4 in molten Mg2 SiO4 as a function of
crystallite radius, r, for different degrees of undercooling,
∆ T , below the melting temperature, T M [12]
∆T , ◦ C: a) 0; b) 10; c) 15; d) 30; e) 50 Crystallites smaller
than the critical radius, r c , redissolve in the melt.
During the crystallization hold, distortion can
arise from gravitational sag of the glass or from
thermal gradients in the furnace. The latter can
cause one portion of the material to crystallize
before the rest. Since most crystalline phases
are denser than the precursor glasses, volume
shrinkage of several percent is typical and must
be accomplished uniformly throughout the arti-
cle. Thermal gradients can arise from improper
furnace design, shadow effects of refractory kiln
furniture, or improper placement of glass arti-
cles. Also, the central portions of massive glass
bodies are slow to heat because of their low ther-
mal conductivity. Moreover with large articles,
heat of crystallization effects can be severe: ther-
mal waves due to exothermic crystallization of
massive articles may cause the central portion to
become up to 50 ◦ C hotter than the other areas
of the ceramming furnace.
To release stresses caused by differential
crystallization, the apparent viscosity of the
glass ceramic should be kept below 1012 P dur-
6 Glass Ceramics
ing crystallization to allow viscous flow and pre-
vent fracturing. To avoid gravitational sag, the
viscosity should have a lower limit which de-
pends on the shape and the size of the article, as
well as on the support in the kiln, but is com-
monly around 1010 P.
Figure 4. Temperature regime for nucleation (a, b) and
growth (c) in the Li2 O · 2 SiO2 system, showing the non-
coinciding temperature domains in which nucleation (low
temperature) and growth (high temperature) tend to occur
a) Theoretical nucleation; b) Experimental nucleation;
c) GrowthThe observed nucleation domain is characteris-
tically narrower than the growth domain. This figure also
indicates that theoretical calculations do not support the ob-
served nucleation behavior in this system (→Glass).
3. Nature of Crystalline Phases
3.1. Metastability
The ceramming (i.e., heating) of glass to produce
glass ceramics can be described as subsolidus
crystallization (i.e., crystallization at a tempera-
ture below which melting occurs). Accordingly,
the expected crystalline phases in glass ceram-
ics are those of an equilibrium subsolidus as-
semblage appropriate for the bulk composition
of the precursor glass and the temperature of the
crystal growth step. However, in many glass ce-
ramic systems, the observed crystalline phases
are metastable. This is not unexpected, because
glass itself is in a metastable state. Thus, with
glass rather than with a melt as the initial state,
crystalline phases can be formed which do not
occur under conditions of “equilibrium crystal-
lization”.
Perhaps the best example of this phenomenon
is the precipitation of β-quartz solid solutions
from lithium aluminosilicate glasses that are ce-
rammed for a short time at about 900 ◦ C. Not
only is the β-quartz metastable at this temper-
ature, it also appears to be thermodynamically
unstable, i.e., this phase is not a member of any
equilibrium assemblage at any temperature for
these bulk compositions. Prolonged heating at
900 ◦ C, or raising the ceram temperature, causes
the β-quartz glass ceramic to invert to a stable
assemblage containing β-spodumene solid solu-
tion (Fig. 5). However, the early formed β-quartz
glass ceramics persist indefinitely when cooled
to room temperature. Moreover, such glass ce-
ramics can withstand indefinite thermal cycling
between room temperature and 900 ◦ C without
undergoing inversion to a β-spodumene glass
ceramic.
Figure 5. Phase transitions in a lithium aluminosilicate
glass as a function of time and temperature
All phases in this system are solid solutions (SS) with vary-
ing silica content.
3.2. Physical Properties
The physical properties rather than the morpho-
logical properties of the crystalline phases tend
to dominate the behavior of a glass-ceramic ar-
ticle.
3.2.1. Thermal Properties
Crystalline phases encompassing a wide range
of thermal expansion coefficients have been
precipitated from glass (Table 2). Glass ce-
ramics containing high-expansion phases such
as nepheline, NaAlSiO4 (expansion coefficient
 Glass Ceramics 7

50×10−6 K−1 ), are commercially important be- expansion coefficient can be increased gradu-
cause they can be strengthened by the appli- ally by partially replacing lithium with magne-
cation of low expansion glazes. Phases with sium or zinc. By taking advantage of this ef-
coefficients of thermal expansion as high as fect, stuffed β-quartz glass ceramics with a wide
12.5×10−6 K−1 (e.g., fluorcanasite) can easily range of thermal expansion coefficients, (−2 to
be precipitated from glass. Crystalline phases +5)×10−6 K−1 can be manufactured.
with ultralow coefficients of thermal expan-
sion are even more important, however, and are
widely used in glass ceramic articles that are sub-
jected to extensive thermal cycling or articles in
which even minor distortion due to thermal fluc-
tuation is undesirable.
The most important of the low-expansion
phases are the lithium aluminosilicates, β-
spodumene (LiAlSi2 O6 ) and β-eucryptite
(LiAlSiO4 ), which can be regarded as “stuffed”
derivatives of the two polymorphs of crys-
talline silica, keatite and β-quartz, respectively.
Keatite consists of a three-dimensional network
of five-membered tetrahedral rings, whereas
β-quartz consists of a three-dimensional net-
work of six-membered tetrahedral rings. The
helical arrangement of silica tetrahedra in both
phases results in unique behavior with increas-
ing temperature; expansion along one crystal
axis is accompanied by contraction along the
perpendicular axes. As a result, the net thermal
expansion of both crystalline silicas is excep-
tionally low. To capitalize on this property in a
glass ceramic body, individual crystals must
be small and unoriented. Solid solutions of
β-spodumene (stuffed keatite, Li2 O – Al2 O3 –
nSiO2 ) have been crystallized from a variety
of lithium aluminosilicate glasses. Important in
most applications of β- spodumene glass ce-
ramics is the fact that thermal expansion can be
tailored to suit a wide range of uses. Volume
thermal expansions and thermal expansion for
the tetragonal axes are illustrated in Figure 6 A
and 6 B, respectively. Whereas bulk expansion
decreases with increasing silica content, the in-
dividual axes show a very large anisotropy in
expansion behavior (Fig. 6 B).
Stuffed derivatives of β-quartz show a wide
range of solid solutions between SiO2 and Figure 6. Thermal expansion in the lithium aluminosilicate
LiAlO2 , Mg (AlO2 )2 , Zn (AlO2 )2 , Li2 BeO2 , system
Al (AlO2 )3 , Li2 ZnO2 , BPO4 , or AlPO4 . This A) Linear expansion for keatite (dashed lines, five-
allows crystallization of ultralow expansion membered rings of silica tetrahedra) and synthetic β-
spodumene (solid lines, 6-membered rings of silica tetra-
phases from a wide variety of glass composi- hedra;
tions. The thermal expansion coefficient of β- B) Volume expansion for β-spodumene solid solutions. The
eucryptite (lithium β-quartz solid solution) is n value represents the silica concentration in the Li2 O –
of the order of −2×10−6 K−1 . The thermal Al2 O3 – nSiO2 system.
8 Glass Ceramics
Table 2. Bulk linear coefficients of thermal expansion of crystalline phases used in glass ceramics [14], [15]

Compound Formula Expansion coefficient 10−6 K−1 Temperature, ◦ C ∗∗

Nepheline NaAlSiO4 50 RT – 500

Anorthite CaAl2 Si2 O8 19 RT – 850
Celsian BaAl2 Si2 O8 3 RT – 600
Mg cordierite Mg2 Al3 AlSi5 O18 7 RT – 800
Commercial cordierite 3 RT – 900
Fluorocanasite Ca5 Na4 K2 Si12 O30 (OH,F)4 12.5 RT – 800
β-Spodumene LiAlSi2 O6 2 RT – 1200
Keatite SiO2 −1 RT – 500
β-Eucryptite LiAlSiO4 1 RT – 450
α-Quartz SiO2 40 RT – 450
SiO2 glass SiO2 50 −23 – 1000
α-GeO2 GeO2 30 RT – 850
β-Quartz SiO2 −6 600 – 900
Pyroxenes (Mg,Fe)2 Si2 O6 32 – 38 RT – 800
Andalusite Al2 Si2 O5 43 RT – 800
Sillimanite Al2 Si2 O5 26 RT – 800
Topaz Al2 SiO4 (F,OH)2 25 RT – 800
Zircon ZrSiO4 18 RT – 800
MgO 15.5 −150 – 1100
ZrO2 10 – 11 RT – 1000
Al2 O3 ∗ 9.4 −150 – 1100
TiO2 ∗ 8.8 −150 – 1100
SiC 5.4 −150 – 1100
Diamond 4.1 −150 – 1100

∗ Polycrystalline samples.
∗∗ RT = room temperature.

The specific heat of glass ceramics varies
only slightly with composition. A characteris-
tic value in the temperature range between 20
and 400 ◦ C is 1000 J kg−1 K−1 , and is similar to
values for glass and conventional ceramics.
The thermal conductivity of glass ceramics
is an important property in such applications as
range tops and cookware. Glass ceramic ma-
terials tend to have higher thermal conductiv-
ity than glass, but lower than ceramics made
from pure oxides. A characteristic value for
lithium aluminosilicate glass ceramics is about
5.5 W m−1 K−1 .
3.2.2. Transparency
Most glass ceramic bodies are opaque. In order
for a glass-ceramic body to be transparent ei-
ther: (1) the dimension of the individual crystals
should be about one third of the wavelength of
visible light, or (2) the refractive index of each
crystal should match the refractive index of the
residual glass and the birefringence of each crys-
tal should be negligible, (i.e., optical isotropy).
The first condition is exemplified by glass ce-
ramics containing mullite (aluminum silicate).
A fine dispersion of mullite can be formed from
glasses in the Al2 O3 – SiO2 system. The result-
ing glass ceramic is clear, even though mullite
is birefringent and has a higher refractive in-
dex than the residual glass. Upon prolonged heat
treatment, crystal size increases and is accompa-
nied by loss of transparency.
The second condition has been achieved in
a number of glass ceramics where the princi-
pal crystalline phase is the stuffed β-quartz solid
solution. Pure β-quartz is an optically uniaxial
positive mineral, but in solid solution its bire-
frigence is negligible at approximately 70 wt %
SiO2 . Crystals of β-quartz containing less than
70 wt % SiO2 are optically negative. The large
number of components in the β-quartz solid so-
lution also allow the composition of the residual
glass to be tailored such that the refractive index
of the crystals matches that of the residual glass,
resulting in transparent glass ceramics. Compo-
sitions of commercial transparent glass ceramics
are shown in Table 6.
3.2.3. Electrical Properties
Resistivity. In commercial glass ceramics,
the dominant crystalline phases are silicates,

aluminosilicates, and phosphates; they can be
broadly classified as electrical insulators. Elec-
trical conduction occurs by diffusion of weakly
bonded ions, primarily alkali-metal ions. At low
temperatures, ionic mobility is negligible and,
consequently, most of these phases are char-
acterized by low electrical conductivity. This,
coupled with the fact the crystalline phases in
glass ceramics are commonly surrounded by a
siliceous residual glass, is responsible for the
high electrical resistivity of most glass ceram-
ics.
Dielectric Constant. The dielectric constant
of most glass ceramics is low, characteristic val-
ues being around 6 at 1 MHz and 20 ◦ C. The
structure of the crystalline phases in these ma-
terials is dominated by the rigid framework of
network-forming components, such as silicate
tetrahedra, which are only slightly polarized by
an applied electric field. Moreover, glass ceram-
ics in which the crystalline phases as well as
the residual glass contain only network-forming
components can have exceptionally low dielec-
tric constants (as well as very high resistivity).
Good examples of such materials are glass ce-
ramics consisting of crystallites of cubic BPO4
within a highly siliceous residual glass; they can
have dielectric constants as low as 4.
Glass ceramics with relatively high electrical
conductivity and/or dielectric constants can be
formed from relatively depolymerized glasses,
i.e., glasses with a high network modifier con-
tent. Crystallization of such glasses can result
in the precipitation of oxide phases, such as
titanates and niobates. For example, glass ce-
ramics containing an interconnected network of
crystallites of titanium suboxides can be formed
from reduced titanium aluminosilicate glasses.
These suboxides are themselves good electrical
conductors and, as they are in grain-to-grain con-
tact, make the glass ceramic itself conductive.
Heat treatment of certain alkaline earth – lead
aluminosilicate glasses can result in the precip-
itation of ferroelectric oxides with a perovskite
structure. In this way, glass ceramics with dielec-
tric constants of the order of 103 can be manu-
factured and utilized in the fabrication of capac-
itors.
Dielectric losses include losses through con-
ductance, ion relaxation, deformation, and vi-
Glass Ceramics 9
bration. Conductance and relaxation losses are
primarily determined by the mobility and con-
centration of the alkali-metal ions present and
predominate at frequencies below 1 MHz. De-
formation and vibration losses are important at
frequencies of about 10 MHz. Characteristic val-
ues for glass ceramic loss factors are around 0.02
at 1 MHz and 20 ◦ C.
Dielectric Strength. The dielectric strength
is important in applications involving the use of
glass ceramics as high-voltage insulators or con-
densers. The very fine-grained, nonporous mi-
crostructure of glass ceramics ensures that they
have a substantially higher dielectric strength
than conventional ceramics with characteristic
values around 47 kV/mm.
3.2.4. Mechanical Properties
Glass ceramics can be considered as brit-
tle glass – crystal composites. Their mechanical
properties are strongly affected by the particle
size and volume fraction of the crystalline phase,
the interfacial bond strength, and differences in
elastic modulus and thermal expansion between
glass and crystallites.
Strength and Elasticity. Glass ceramics are
stronger than the parent glasses. In glasses, the-
oretical strengths cannot be achieved due to the
presence of intrinsic and/or extrinsic flaws. In
atomic terms, flaws may be regarded as “sharp
cracks” or radii that act as stress concentrators.
The strength of the material is inversely pro-
portional to the critical flaw dimension. A com-
monly used model developed by Griffith states
that
σ= (2Eγ/πc)1/2 (12)
where σ is the strength, E is the modulus of elas-
ticity, γ is the fracture surface energy, and c is the
length of the crack (flaw). Stress is proportional
to the square root of the flaw size and cracks
grow rapidly when the stress (due to mechan-
ical or thermal loading) overcomes the atomic
bonding forces that hold the material together.
For most brittle oxide solids, three types of
flaw can be identified: surface cracks, internal
10 Glass Ceramics
processing defects, (e.g., porosity), and environ-
mentally induced damage. Strength and tough-
ness (resistance to crack propagation) of crys-
talline brittle materials depend on grain bound-
ary residual stress, the ratio of flaw dimensions
to grain size, crystallite cleavage resistance, per-
cent crystallinity, crystallite size, and relative
elastic properties. Many of these issues are over-
come in glass ceramics through the creation
of highly crystalline microstructures which are
specifically designed to resist crack propagation
by increasing material toughness.
One method used to increase the toughness of
glass ceramics is modification of crystallite size.
If the length of the microcrack c is assumed to be
proportional to the crystal diameter, then from
the Griffith equation the strength σ is approxi-
mately inversely proportional to the square root
of the crystal size d
1
σ∼ √ (13)
d
Thus, small crystallites increase the strength of
the glass ceramic.
Additional toughening occurs when the glass
ceramic contains a crystalline phase that is
stronger than the glass matrix. This is generally
the case because, at an atomic level, the crys-
tals which precipitate from the glass are tightly
packed so that the number of bonds to be broken
per unit volume is large and the modulus of elas-
ticity is high. The size of the microcracks is then
limited to the region between crystals and the
critical parameter of mechanical strength will
be the mean free path in the residual glass L s :
Ls =d (1 − Vf ) /Vf (14)
where V f is the volume fraction of the crystalline
phase. A small mean free path indicates a major
strength improvement due to deflection tough-
ening of crack tips.
Hardness. The hardness of glass ceramics
can vary significantly depending upon the com-
position of the crystalline phases. Knoop values
in excess of 10 000 MPa can be obtained in glass
ceramics where the dominant phase is mag-
netite (Fe3 O4 ), spinel (MgAl2 O4 ), or sapphirine
(Mg2 Al4 SiO10 ). This permits use of glass ce-
ramics in applications where high abrasion re-
sistance is required.
3.2.5. Durability
The chemical stability and durability of glass
ceramics are affected by the composition of the
crystalline phase, as well as the amount and
composition of the residual glass. For example,
a primary cause of poor chemical durability is
the presence of alkali-metal ions in the residual
glass. Many aluminosilicate glass ceramics con-
tain phases that are extremely siliceous, such as
β-spodumene and mullite; this results in excep-
tional resistance to chemical etching and stain-
ing.
3.3. Microstructure
The texture of the crystalline assemblage is one
of the principal factors determining the physical
properties of glass ceramics, ranking in impor-
tance only second to the physical properties of
the dominant precipitating phase. Changes in the
mechanism and rate of nucleation and growth
affect crystal morphology, permitting the devel-
opment of myriad textures, which are often dis-
tinct from normal textures characteristic of sin-
tered powders or fusion-cast materials. Key mi-
crostructures of commercial glass ceramics are
described as:
1) ultrafine-grained
2) relict
3) “coast and island”
4) “house of cards”
5) acicular interlocking
6) dendritic
Ultrafine-Grained Textures. The Voronoi
patterns (Fig. 1) have shown how ultrafine-
grained textures can be achieved: the greater the
number of nucleation sites, the finer the precip-
itate and, as shown in Section 3.2, the better the
mechanical strength. In the lithium aluminosil-
icate system, these textures can be obtained by
adding roughly equivalent amounts (on a mo-
lar basis) of TiO2 and ZrO2 to the glass. Small
(<10 nm) zirconium titanate crystallites precip-
itate when such glasses are heated to about 50 ◦ C
above the glass transition temperature. These
crystallites form a uniform dispersion through-
out the residual glass, providing a multitude of

nucleation sites for the epitaxial growth of the
stuffed β-quartz solid solution. The efficient nu-
cleation, coupled with sluggish grain growth, al-
lows the crystals to grow only to about 50 nm in
diameter before impinging upon one another.
Relict Textures. Some glass-ceramic mi-
crostructures mimic the texture of the precursor
glass. This is, for instance, the case in mullite
glass ceramics where the original glass sepa-
rates into aluminous droplets within a siliceous
matrix. When heated above the annealing point
of the phase-separated glass, the alumina-rich
droplets become more fluid than the matrix and
crystallize rapidly to mullite. The mullite crys-
tals are restricted by the shape of the original
droplet and reflect its morphology. Due to the
small size of the mullite “droplets” (<0.1 µm),
these glass ceramics are transparent.
Relict microstructures can also develop when
a crystal phase retains the morphology of a
metastable, crystalline precursor. For example,
a relict dendritic texture (see below) is observed
in photoetched lithium disilicate glass ceram-
ics. The crystals reflect the dendritic texture in-
herited from metastable lithium metasilicate, the
first crystalline phase formed upon ceramming.
“Coast and Island” Texture. A coast and
island texture usually develops when an equi-
librium crystal phase forms at the expense of
a metastable assemblage of phases. An exam-
ple is the growth of hexagonal cordierite in
magnesium aluminosilicate glass ceramics at
the expense of α-quartz, sapphirine, and spinel.
Growth of hexagonal cordierite is initiated at
boundaries between grains of the latter phases,
and cordierite gradually becomes the dominant
phase. Any excess silica crystallizes as cristo-
balite laths, which along with early-formed ru-
tile, become partially or wholly enveloped by the
cordierite. This results in an interlocking struc-
ture with good mechanical strength and tough-
ness.
“House of Cards” Texture. The precision
machinability of fluoromica glass ceramics such
as Macor, with conventional metal-working
tools is due to the “house of cards” texture, which
is characterized by randomly oriented, flexible
flakes. In the case of fluoromica glass ceramics,
the plate-like crystallites have low shear strength
Glass Ceramics 11
due to their perfect basal cleavage and thus tend
to either arrest fractures or cause deflection or
branching of cracks. Another important property
dependent on this microstructure is high dielec-
tric strength. Such insulating qualities are possi-
ble because of the continuous interlocking of the
mica sheets. Very low helium permeation rates,
important in high vacuum applications, are also
related to this microstructure.
Acicular Interlocking Texture. Interlock-
ing rod- or blade-like crystals in glass ceramics
can serve as important strengthening and tough-
ening agents. Most chain silicate glass ceramics
contain crystallites with this morphology. The
high toughness is attributed to rod reinforce-
ment by elongated amphibole crystals such as
potassium fluororichterite.
An even tougher microstructure is developed
in the highly crystalline monophase glass ce-
ramics which consist of interpenetrating blades
of fluorcanasite. Cleavage splintering can be ob-
served, causing energy absorption through crack
branching and deflection.
Dendritic Textures. The dendritic mi-
crostructure is characterized by the presence
of crystallites with skeletal morphology, which
is associated with very high surface energies.
Snow crystals are familiar examples of dendritic
crystals. Glass ceramics with dendritic textures
typically contain a relatively high percentage of
residual glass, due to inefficient crystal packing.
The texture assumed by lithium metasilicate
crystallites in the chemically etchable glass ce-
ramic Fotoform is an example of the dendritic
microstructure. The metasilicate dendrites form
a continuous three-dimensional lacework. The
glass ceramic can be etched with hydrofluoric
acid, which attacks the low silica crystallites at a
far higher rate than the durable aluminosilicate
residual glass.
4. Types of Glass Ceramics
Useful glass ceramics are generally silica-con-
taining glasses and can be classified in three
groups: silicates, aluminosilicates, and fluorosil-
icates. Some of the more important systems cur-
rently used in the manufacture of commercial
glass ceramics are shown in Table 3.
12 Glass Ceramics

Table 3. Silicate glass ceramic systems

System Advantages

Silicate
Li2 O – SiO2 photoetching capability
Aluminosilicate In lithium silicate glasses, the photoinduced,
Li2 O – Al2 O3 – SiO2 very low thermal thermally developed silver speck acts as a nu-
expansion
cleation site for the epitaxial growth of dendritic
MgO – Al2 O3 – SiO2 good mechanical, thermal,
and dielectric properties metasilicate (Li2 SiO3 ), which is more readily
Na2 O – Al2 O3 – SiO2 high mechanical strength etched by hydrofluoric acid than the high-silica
from compression glazing
parent glass. Growth of lithium metasilicate oc-
CaO – MgO – Al2 O3 – SiO2 low cost
Fluorosilicate curs selectively only in those areas which have
K2 O – MgO – Al2 O3 – SiO2 – F machinability been exposed to UV radiation. Using masking
techniques, complex patterns of lithium metasil-
icate can be formed in these glasses. The irradia-
tion pattern can then be selectively etched out of
the glass with hydrofluoric acid, forming the ba-
4.1. Silicate-Based Glass Ceramics sis for Fotoform articles. (See also → Imaging
Technology). The photoetched glass is flood-
The compositions of some silicate-based glass
exposed to UV radiation and recerammed at
ceramics are listed in Table 4.
higher temperature, resulting in the inversion of
Table 4. Composition of commercial silicate glass ceramics (mol %) metastable lithium metasilicate to the stable dis-
ilicate, Li2 Si2 O5 . The resulting glass ceramic
Component Fotoform/ “Slag-sital” “Minelbite”
Fotoceram white, Soviet gray, is strong, with an abraded modulus of rupture
Corning 8603 Union Hungary around 150 MPa, and negatively replicates the
SiO2 75.8 56.3 63.8 original irradiation pattern to a resolution of less
Al2 O3 2.2 5.0 8.8 than 0.1 mm.
Li2 O 17.8
Na2 O 1.5 5.3 3.3
Applications of such photosensitive glass ce-
K2 O 2.5 0.4 1.3 ramics include recording head pads, fluidic de-
MgO 3.3 8.9 vices (e.g., hydraulic networks), cellular face
CaO 27.0 10.1 plates for gas discharge displays, and charged
ZnO a 1.0
MnO a 0.8 1.8
plates for ink-jet printing.
Fe2 O3 a 0.1 1.0
Sa 0.8 1.2 Calcium and Calcium Magnesium Sili-
CeO2 b 0.0047
cates. Blast furnace slags have been used since
SnO2 b 0.0011
Sb2 O3 c 0.079 the 1970s in eastern Europe to manufacture in-
Ag a 0.06 expensive glass ceramics. Compositions of two
Au a 0.00029 glass ceramics of this type are given in Ta-
a
Nucleant. ble 4. The furnace slags are rolled as sheets
b
Sensitizing agent. or cast as tiles and used for both interior and
c
Fining agent. exterior use. The slag is remelted at around
1450 ◦ C, formed into a glass and subsequently
heat treated at about 1000 ◦ C. The crystalline
Lithium Silicates. Photosensitive lithium phases diopside [14483-19-3] (CaMgSi2 O6 ) or
silicate glass ceramics (e.g., Fotoform/ Foto- wollastonite [13983-17-0] (CaSiO3 ) nucleate
ceram, Corning) include a noble metal such heterogeneously on zinc, iron, or manganese sul-
as gold or, more commonly silver, and triva- fide particles. These alkaline-earth silicates form
lent cerium ions (Table 4). Upon exposure to fine, 1 – 5 µm, equiaxial grains in a matrix of
UV light, Ce3+ is thought to act as an electron residual aluminosilicate glass, and confer good
donor, ultimately leading to the precipitation of abrasion resistance and chemical durability on
metallic silver: the glass ceramic. The glass ceramics have a va-

riety of applications depending on their com-
position. Their main uses are in the construc-
tion and chemical or petrochemical industries as
abrasion-resistant or chemically resistant floor
and wall coverings, chimneys, parts of chemical
pumps, and funnels.
Magnesium Silicates. Glass ceramics based
on enstatite [14681-78-8] (MgSiO3 ) are of sci-
entific interest because of the martensitic (i.e.,
dilatational) transformation from protoenstatite
to clinoenstatite upon cooling. This transforma-
tion results in fine lamellar (i.e., parallel) twin-
ning which produces a superior crack-tip blunt-
ing texture in the body. Dilution of enstatite glass
with other components is required because pure
magnesium metasilicate does not form a stable
glass. Two representative compositions from the
SiO2 – MgO – Al2 O3 – Li2 O – ZrO2 and SiO2 –
MgO – ZrO2 systems are given in Table 5. These
refractory, tough, fine-grained glass ceramics
consist of 50 – 85 wt % enstatite with zircon
(ZrSiO4 ) and β-spodumene, (LiAlSi2 O6 ), or
tetragonal zirconia (ZrO2 ) as additional phases.
Table 5. Compositions and properties of enstatite (MgSiO3 ) glass
ceramic
Parameter E-1
Composition, mol %
SiO2 55.0
MgO 35.3
Al2 O3 3.0
Li2 O 1.7
ZrO2 4.9
Ceramming schedule 800 ◦ C, 2 h
1200 ◦ C, 4 h
193 ± 15
Abraded (modulus of
rupture, MPa)
Fracture toughness, MPa m1/2 3.5 ± 0.4
Refractory temperature, ◦ C 1250
Coefficient of thermal
expansion (0 – 1000 ◦ C), K−1 68×10−7
During the ceramming sequence, phase sep-
aration occurs between 800 and 900 ◦ C and is
followed by rapid crystallization of tetragonal
zirconia. These zirconia crystallites form the nu-
cleation centers on which enstatite precipitates.
At temperatures above 1200 ◦ C, zircon is formed
by reaction of zirconia with unpolymerized sil-
ica present in the residual glass, thereby further
stabilizing the glass ceramic.
Glass Ceramics 13
The toughest (about 4 MPa m1/2 ) and
most refractory compositions are basically two-
phase enstatite – zircon glass ceramics (type E-
2). These have use temperatures approaching
1525 ◦ C, the eutectic temperature in the SiO2 –
MgO – ZrO2 system. They are well-suited for
high-temperature applications.
4.2. Aluminosilicate Glass Ceramics
Lithium and magnesium aluminosilicate glass
ceramics are currently the principal commercial
glass ceramic systems. Their utility lies in their
resistance to thermal shock combined with ex-
cellent chemical durability.
The Li2 O – Al2 O3 – SiO2 system has pro-
duced glass ceramics with exceptionally low
thermal expansion coefficients based on either
β-quartz or β-spodumene solid solution. These
phases can be melted and quenched to a sta-
ble glass permitting the manufacture of virtu-
ally monophase β-quartz or β-spodumene glass
ceramics which contain only minor amounts of
nucleant phases and residual glass. Glass ce-
ramics containing β-quartz or β-spodumene can
be made from glasses of the same composition
E-2
by modifying the heat treatment: β-quartz is
formed by ceramming at or below 900 ◦ C, and
β-spodumene by ceramming above 1000 ◦ C.
49.3
44.9 β-Quartz Solid Solution. The composition
of the β-quartz solid solution is (Li2 O, RO) ·
5.8 Al2 O3 · nSiO2 , in which n varies between 2
800 ◦ C, 2 h and 10 and R is a divalent cation, commonly
1400 ◦ C, 4 h Mg2+ or Zn2+ ; the stoichiometric end member,
200 ± 15
LiAlSiO4 , is called β- eucryptite. For commer-
4.6 ± 0.6 cial glass ceramics, n ranges between 6 and 8
1500 because the high silica content of these compo-
sitions furnishes a melt that is sufficiently vis-
80×10−7
cous to be rolled, pressed, blown, and vacuum
formed. Representative compositions are listed
in Table 6.
A phase with the fluorite structure, ZrTiO4 ,
has proven to be the most effective nucleating
agent in precipitating β-quartz from lithium alu-
minosilicate glasses. Very fine crystallites with
grain sizes of the order of 60 nm can be produced
if the nucleant concentration is ca. 4 wt %.
The combination of transparency, low ther-
mal expansion behavior, optical polishability,
14 Glass Ceramics

and strength greater than glass has generated ap- The ceram schedule attains a maximum near
plications such as see-through cookware, tele- 1125 ◦ C, about 100 ◦ C below the liquidus tem-
scope mirror blanks, woodstove windows, IR- perature. At least 93 vol % of the material is crys-
transmitting range tops, optically stable plat- talline, with β-spodumene being the dominant
forms, and ring-laser gyros. phase. Spinel, rutile, and residual glass are sec-
ondary phases. The glass ceramic is produced as
Table 6. Composition (mol %) of transparent glass ceramics based
on β-quartz solid solution a honeycomb product for a turbine engine heat
exchanger. It is made from a powdered glass
Component Visions Zerodur Narumi
(Corning) (Schott) (Nippon
frit, which as slurry impregnates paper wound
Electric) on a wheel as alternately corrugated sheets. Af-
ter firing, a porous ceramic regenerator wheel is
SiO2 74.2 63.8 70.6 produced which allows energy to be transferred
Al2 O3 12.2 17.1 14.4 from hot exhaust gases to the cold intake air in
Li2 O 5.8 8.6 9.2 the turbine engine.
MgO 2.9 1.7 0.8
ZnO 0.8 1.2
P2 O 5 3.8 0.6
Cordierite-Based Glass Ceramics. The
F 0.3 hexagonal (high temperature) polymorph of
Na2 O 0.2 0.6 0.6 cordierite [1302-88-1] (Mg2 Al4 Si5 O18 ) is the
K2 O 0.1 0.2 principal crystalline phase in magnesium alu-
BaO 0.3
TiO2 2.2 2.0 1.6
minosilicate glass ceramics. These materials
ZrO2 0.9 1.1 1.2 are strong, have excellent dielectric properties,
As2 O3 0.3 0.2 0.4 and good thermal stability and shock resistance.
Fe2 O3 0.04 0.01 0.01
The thermal expansion of cordierite is low and
anisotropic, the c axis expanding, and the a and
b axes contracting, resulting in virtually zero
β-Spodumene (Keatite) Solid Solu- volume expansion.
tion. Two representative compositions of β- In these materials, hexagonal cordierite crys-
spodumene glass ceramics are given in Ta- tallizes together with cristobalite, rutile, and
ble 7. Comparison with the Vision composi- magnesium dititanate; a small amount of resid-
tion in Table 6 indicates the similarity between ual glass is isolated at the grain boundaries.
β-spodumene and β-quartz glass ceramic mate- This glass ceramic is used for missile radomes.
rials. A representative glass ceramic composition,
together with selected physical properties, is
Table 7. Composition and properties of glass ceramics based on
keatite (β-spodumene) solid solution shown in Table 8.
Parameter Corning Ware Cercor Corning

Composition, mol % Table 8. Composition and properties of commercial cordierite glass

SiO2 73.6 75.9 ceramic (Corning 9606)
Al2 O3 11.0 13.6
Parameter Value Phases
Li2 O 5.9 10.5
MgO 4.1 Composition, mol %
ZnO 0.8 SiO2 58.1
Na2 O 0.4 Al2 O3 12.1
K2 O 0.1 MgO 22.6 cordierite
TiO2 3.7 CaO 0.1 cristobalite
ZrO2 0.1 TiO2 6.9 rutile
Fe2 O3 0.1 As2 O3 0.1 Mg-dititanate
As2 O3 0.2 Fe2 O3 0.1
Coefficient of thermal 1.2×10−6 0.5×10−6 Coefficient of thermal
expansion, K−1 (0 – 500 ◦ C) (0 – 1000 ◦ C) expansion, K−1 4.5×10−6
Abraded flexural 100 Fracture toughness, MPa m1/2 2.2
strength, MPa Thermal conductivity,
J s−1 cm−1 K−1 0.37
Knoop hardness, MPa 7000
Corningware is made from a multicompo- Dielectric constant (8.6 GHz) 5.5
nent glass containing TiO2 as nucleating agent. Loss tangent 0.0003

Sodium Aluminosilicates. Fine-grained
glass ceramics, containing nepheline
[12251-27-3] (NaAlSiO4 ) can be formed from
glasses in the Na2 O – Al2 O3 – SiO2 – TiO2 sys-
tem. Nepheline is a stuffed derivative of
tridymite, a high-temperature polymorph of
silica. Titanium dioxide acts as an internal nu-
cleating agent and opacifier, and crystallizes as
anatase in the cerammed material. These glass
ceramics have thermal expansion coefficients
around 5×10−6 K−1 , near that of nepheline,
reflecting the expansion behavior of tridymite.
A typical composition of this glass ceramic is
given in Table 9.
Table 9. Nepheline glass ceramic tableware (Pyroceram 9609)
Oxide Content, Phases
mol %
SiO2 53.0
Al2 O3 21.4
Na2 O 16.0 nepheline (NaAlSiO4 )
BaO 2.6 celsian (BaAl2 Si2 O8 )
TiO2 6.0 anatase (TiO2 )
As2 O3 0.4 glass
Barium is added to promote the formation of
celsian (BaAl2 Si2 O8 ), which has a lower ther-
mal expansion coefficient (3×10−6 K−1 ) than
nepheline, thereby improving thermal shock re-
sistance. The glass ceramics are used in a wide
variety of products ranging from coverings for
microwave antennas, large electric insulators,
and miniature vacuum tubes to heat-resistant
kitchenware and stove hotplates.
Other Aluminosilicate Systems. Glass ce-
ramic systems based on mullite [55964-99-3]
(3Al2 O3 · 2SiO2 ) can be produced from mod-
ified binary Al2 O3 – SiO2 glasses. Transparent
mullite glass ceramics, doped with ions such as
Cr3+ have unique luminescent characteristics.
Calcium aluminosilicate glass ce-
ramics based on anorthite [1302-54-1]
(CaO · Al2 O3 · 2SiO2 ) can be formed by sur-
face crystallization sintering of glass frit. They
form ideal glass ceramic matrices for silicon
carbide fiber-reinforced composites. The good
thermal stability of anorthite (up to 1500 ◦ C),
combined with its close match in thermal expan-
sion with silicon carbide makes this composition
particularly attractive.
Glass Ceramics 15
Glass ceramics belonging to the cesium
aluminosilicate system are highly refractory.
Glass ceramics made from pollucite [1308-53-8]
(Cs2 O · Al2 O3 · 4SiO2 ) and mullite crystallized
at 1600 ◦ C have a thermal stability that is 350 ◦ C
higher than that of fused silica. Due to their re-
fractory nature, these materials must be melted
at 1900 ◦ C and formed near 1800 ◦ C.
4.3. Fluorosilicate Glass Ceramics
Two classes of glass ceramics fall in this cat-
egory: (1) fluorosilicate micas consisting of
sheets of silica tetrahedra and (2) fluoroinosil-
icates, whose structure is based on double or
quadruple chains of silica tetrahedra.
Fluormica Glass Ceramics. Fluormica
sheet silicates provide machinable glass ce-
ramics which can be turned, drilled, milled,
or threaded using conventional metal-working
machines.
Macor is a commercial glass ceramic
based on fluorophlogopite [12003-38-2]
(KMg3 AlSi3 O10 F2 ). Due to its high fluorine
content, stable glasses with fluorophlogopite
composition cannot be formed. Addition of
B2 O3 and SiO2 , as shown in Table 10, results in
stable glass. The Macor composition is melted
to an opal glass that is subsequently crystal-
lized by heating to 950 ◦ C. During ceramming,
metastable chondrodite, 2 Mg2 SiO4 · MgF2 , is
the first phase to precipitate from the glass, crys-
tallizing from the magnesium-rich matrix at the
surface of the aluminosilicate droplets that con-
stitute the rest of the parent opal. Chondrodite
is subsequently transformed into norbergite,
Mg2 SiO4 · MgF2 , which in turn reacts with the
residual glass to form fluorophlogopite and some
mullite.
The mica structure is particularly well
adapted for machinability due to the rapid propa-
gation of fracture in the plane of the silica sheets.
Furthermore, the “house of cards” texture of flu-
orophlogopite glass ceramics (see Section 3.3)
increases the tortuosity of the fracture path and,
hence, fracture energy is rapidly dissipated. The
machinability of Macor also benefits from the
relatively coarse size of the mica flakes. Glass
ceramics with small crystallites are less easy to
machine than those with large crystallites; the
16 Glass Ceramics
difference is presumably due to the additional
energy required to cleave many more crystal-
lites.
Table 10. Commercial fluormica glass-ceramic compositions
(mol %)
Oxide Macor
SiO2 42.2
B2 O3 6.6
Al2 O3 8.8
MgO 19.3
K2 O 5.4
F 17.8
ZrO2
CeO2
Mica type
Macor K1 − x Mg3 Al1 − x Si3 + x O10 F2
Dicor K1 − x Mg2.5 + x /2Si4 O10 F2
x < 0.2
Macor has been employed in a wide range of
applications, including precision electrical insu-
lators, vacuum feedthroughs, windows for mi-
crowave tube parts, sample holders for field ion
microscopes, seismograph bobbins, gamma-ray
telescope frames, and boundary retainers on the
space shuttle. The precision machinability of
Macor with conventional metal-working tools,
its high dielectric strength (40 kV/nm), and very
low helium permeation rates are particularly im-
portant in high-vacuum applications.
Fluorosilicate glass ceramics based on
tetrasilicic micas, such as KMg2.5 Si4 O10 F2 ,
have been developed for use in dental restora-
tion. Tetrasilicic fluormica glass ceramics, mar-
keted under the trade name Dicor, have improved
chemical durability and translucency relative to
Macor. Good strength (∼150 MPa) is associated
with the development of anisotropic flakes at rel-
atively high temperature (>1000 ◦ C). Translu-
cency is achieved by nearly matching the re-
fractive indices of the fluormica and residual
glass, while simultaneously maintaining a fine
(∼1 µm) crystal size. Cerium is added to sim-
ulate the fluorescent character of natural teeth.
The glass ceramic may be cast accurately using a
lost wax technique and conventional dental lab-
oratory molds. The high strength and low ther-
mal conductivity of these materials provide ad-
vantages over conventional metal – ceramic sys-
tems.
Chain Fluorosilicates. Natural nephrite-
jade is renowned for its toughness (i.e., re-
sistance to fracture) due to crack tip blunting
by randomly oriented acicular crystallites. Two
chain fluorosilicates can produce glass ceramics
with similar high toughness: potassium fluor-
Dicor richterite and fluorcanasite.
Potassium Fluorrichterite. The crys-
46 – 57 tal structure of potassium fluorrichterite
KNaCaMg5 Si8 O22 F2 , consists of double chains
0–1
22 – 23
of silica tetrahedra. An optimized fluorrichterite
8–9 glass-ceramic composition in mole percent is:
13 – 21
0–1 SiO2 59.2
0.02 Al2 O3 1.1
MgO 18.5
CaO 4.4
Na2 O 2.5
K2 O 2.7
Li2 O 1.3
BaO 0.1
P2 O 5 0.4
F 9.7
In the early stages of the ceramming of a
fluorrichterite glass, an amorphous emulsion
is formed in which one of the two phases
has a similar composition to tetrasilicic fluo-
rmica, K(Mg2+x Li1 − 2x )Si4 O10 F2 . This phase
crystallizes rapidly at 600 ◦ C and incorporates
most of the network modifiers in the system,
thereby significantly increasing the viscosity
of the residual glass. Precipitation of diopside
(CaMgSi2 O6 ) follows above 700 ◦ C. Fluormica
and diopside subsequently react above 850 ◦ C
with the residual glass to produce the stable as-
semblage potassium fluorrichterite and cristo-
balite, the latter phase growing above 900 ◦ C.
The residual glass is enriched in silica, alu-
mina, and P2 O5 , resulting in exceptional overall
chemical durability. The high thermal expansion
coefficient of this glass ceramic allows the de-
velopment of compressive strength through con-
ventional glazing techniques. Thus, the flexural
strength of these glass ceramics (150 ± 15 MPa)
can be increased to 200 ± 15 MPa. Glazed fluor-
richterite glass ceramics have a translucency and
gloss comparable to those of bone china. This
glass ceramic is currently being manufactured
as high-performance institutional tableware and
mugs for the retail Corelle line.
Fluorcanasite Glass Ceramics. Fluorcana-
site, Ca5 Na4 K2 Si12 O30 (OH,F)4 , has a crystal

structure that is characterized by four intercon-
nected silica chains running parallel to the b axis,
thereby forming a tube. Potassium and sodium
ions are located centrally in the tubes, which are
interconnected by a network of edge-sharing,
calcium and sodium oxyfluoride octahedra.
Fluorcanasite has been crystallized from
glasses. It is nucleated by crystallites of CaF2
and grows in spherulitic fashion on these nu-
clei. Fluorcanasite glass ceramics can be highly
crystalline and virtually monophase. They have
flexural strengths near 300 MPa, a modulus of
elasticity near 80 GPa, and a thermal expansion
coefficient near 12.5×10−6 K−1 . The strain rup-
ture is about 0.35, a high value for a silicate
material. The measured fractured toughness is
5.0 MPa m1/2 , indicating a fracture surface en-
ergy of approximately 150 J/m2 , higher than that
for natural nephrite-jade.
Glass with a fluorcanasite composition can be
rolled, pressed, or cast. Ceramming can be com-
pleted below 900 ◦ C in less than 1 h. Due to their
low silica content, fluorcanasite glass ceramics
are inferior in chemical durability to soda – lime
glass, but superior to many other building ma-
terials. Potential applications for fluorcanasite
glass ceramics include architectural cladding,
interior partitioning, thin housewares, and mag-
netic memory disk substrates.
Fotoform, Fotoceram, Visions, Corning
Ware, Cercor, Pyrocam, Macor, Dicor, Corelle,
Zerodur, and Narumi are registered trade marks.
Glass Fibers → Fibers, 5.Synthetic Inorganic
Glass Wool → Fibers, 5.Synthetic Inorganic
Glassy Metals → Metallic Glasses
Globulins → Blood
Glass Ceramics 17
5. References
1. G. H. Beall: “Design of Glass Ceramics” in H.
Jain, A. R. Cooper, K. J. Rao, D. Chakravorty
(eds.): Trends in Science and Technology of
Glass, World Scientific Press, Singapore 1989.
2. G. H. Beall, R. C. Doman: “Glass-ceramics,”
in: Encyclopedia of Science and Technology,
vol. 6, Academic Press, New York 1987,
pp. 21 – 35.
3. G. H. Beall, Adv. Ceram. 18 (1986) 157 – 173.
4. G. H. Beall, H. L. Rittler, Adv. Ceram. 4
(1982) 301 – 312.
5. W. Vogel: Chemistry of Glass, The American
Ceramic Society, Columbus, Ohio, 1985,
pp. 325.
6. G. P. Smith, Mater. Des . 10 (1989) no. 2,
44 – 63.
7. Z. Strnad, Glass: Sci. Technol. 8 (1986) 268.
8. M. H. Lewis (ed.): Glasses and Glass
Ceramics, Chapman and Hall, London – New
York 1989, p. 378.
9. P. F. James, Adv. Ceram. 4 (1982) 1 – 29.
10. D. Kashiev, Surf. Sci. 14 (1969) 209 – 220.
11. J. E. Dickinson, P. C. Hess, Geochim.
Cosmochim. Acta 49 (1985) 2289 – 2296.
12. I. S. E. Carmichael, F. J. Turner, J. Verhoogen,
Igneous Petrology, McGraw-Hill, New York
1974.
13. K. A. Jackson, Prog. Solid State Chem. 4
(1967) 53 – 80.
14. M. F. Hochella, G. E. Brown, J. Am. Ceram.
Soc. 69 (1986) 13 – 18.
15. L. Cartz, J. D. Jorgensen in : D. C. Larson
(ed.): Thermal Expansion 7, Chicago, Illinois,
Plenum Press, New York 1982, pp. 147 – 154.
 Glass 1

Glass
Glass Ceramics and Metallic Glasses are separate keywords.

Bernard H. W. S. De Jong, Corning Incorporated, Corning, New York 14831, United States (Chaps. 1– 4, and
7)
Ruud G. C. Beerkens, Eindhoven University of Technolgy, Eindhoven, The Netherlands (Chaps. 5, 6, and 8)
Peter A. van Nijnatten, TNO Institute of Applied Physics, Eindhoven, The Netherlands (Chaps. 5, 6, and 8)

1. Definition and Historical Sum- 4.12.2. Refractive Index, Dispersion, and

mary . . . . . . . . . . . . . . . . . . . 3 Optical State . . . . . . . . . . . . . . 42
2. Structure of Glass . . . . . . . . . . 6 4.12.3. Temperature Dependence of Refrac-
2.1. Structure of Special Melts and tive Index . . . . . . . . . . . . . . . . 44
Glasses . . . . . . . . . . . . . . . . . . 8 4.12.4. Stress Optical Coefficients . . . . . . 44
2.2. Composition of Glass . . . . . . . . 10 4.12.5. Radiation Effects . . . . . . . . . . . . 45
2.2.1. Single-Component Glass . . . . . . . 10 4.13. Color of Glasses . . . . . . . . . . . . 46
2.2.2. Silicate Glasses with Two Compo- 5. Production of Glass . . . . . . . . . 49
nents . . . . . . . . . . . . . . . . . . . 12 5.1. Raw Materials . . . . . . . . . . . . . 49
2.2.3. Borate, Phosphate, and Germanate 5.1.1. Chemical Impurities and Decol-
Glasses . . . . . . . . . . . . . . . . . . 15 oration . . . . . . . . . . . . . . . . . . 52
2.2.4. Borosilicate and Aluminosilicate 5.1.2. Waste Glass (Cullet) . . . . . . . . . 53
Glasses . . . . . . . . . . . . . . . . . . 17 5.1.3. Preparation of Raw Materials . . . . 54
2.2.5. Lead Silicate Glasses . . . . . . . . . 18 5.2. Melting Units . . . . . . . . . . . . . 54
2.2.6. Chalcogenide Glasses . . . . . . . . . 18 5.2.1. Flat Glass and Container Glass
2.2.7. Halide Glasses . . . . . . . . . . . . . 19 Tanks . . . . . . . . . . . . . . . . . . . 55
2.2.8. Glasses with Complex Composition 19 5.2.2. Unit Melters . . . . . . . . . . . . . . 58
3. Glass Formation, Crystallization, 5.2.3. All-Oxygen-Fired Melters . . . . . . 58
and Liquid Immiscibility . . . . . . 19 5.2.4. Electrical Melting Units . . . . . . . 59
4. Chemical, Mechanical, and Phys- 5.2.5. New Melter Designs . . . . . . . . . 60
ical Properties of Industrially Im- 5.2.6. Pot Furnaces and Day Tanks . . . . 60
portant Melts and Glasses . . . . . 23 5.3. Melting, Fining, and Homogeniza-
4.1. Rheological Properties of Glass tion . . . . . . . . . . . . . . . . . . . . 61
Melts . . . . . . . . . . . . . . . . . . . 27 5.4. Energy-Saving Technologies . . . 62
4.1.1. Temperature Dependence of Viscos- 5.5. Glass Cooling . . . . . . . . . . . . . 63
ity . . . . . . . . . . . . . . . . . . . . . 28 5.6. Heating and Regulating Glass
4.1.2. Time Dependence of Viscosity . . . 29 Melts . . . . . . . . . . . . . . . . . . . 64
4.1.3. Composition Dependence of Viscos- 5.7. Refractory Lining of Melting
ity . . . . . . . . . . . . . . . . . . . . . 29 Units . . . . . . . . . . . . . . . . . . . 65
4.2. Surface Tension . . . . . . . . . . . . 31 5.8. Vapor-Deposited Glasses . . . . . . 66
4.3. Density . . . . . . . . . . . . . . . . . 31 5.9. Occupational Health . . . . . . . . 66
4.4. Thermal Expansion . . . . . . . . . 32 6. Forming . . . . . . . . . . . . . . . . . 70
4.5. Elastic Properties . . . . . . . . . . . 35 6.1. Hand Forming . . . . . . . . . . . . . 71
4.6. Mechanical Strength . . . . . . . . 35 6.1.1. Blowing . . . . . . . . . . . . . . . . . 71
4.7. Hardness . . . . . . . . . . . . . . . . 36 6.1.2. Pressing . . . . . . . . . . . . . . . . . 72
4.8. Thermal Properties . . . . . . . . . 36 6.1.3. Blowing Combined with Pressing . 73
4.9. Electrical Properties . . . . . . . . . 37 6.1.4. Drawing . . . . . . . . . . . . . . . . . 73
4.10. Gas Permeability . . . . . . . . . . . 39 6.1.5. Redrawing . . . . . . . . . . . . . . . . 75
4.11. Chemical Stability and Surface 6.1.6. Casting . . . . . . . . . . . . . . . . . . 75
Properties . . . . . . . . . . . . . . . . 39 6.1.7. Fritting . . . . . . . . . . . . . . . . . . 76
4.12. Optical Properties . . . . . . . . . . 41 6.1.8. Flat Glass Forming . . . . . . . . . . 76
4.12.1. Transmission, Absorption, and Re- 6.1.8.1. Pilkington Float Process . . . . . . . 76
flection . . . . . . . . . . . . . . . . . . 42 6.1.8.2. Rolling . . . . . . . . . . . . . . . . . . 76

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 365
2 Glass
6.1.8.3. Overflow Process . . . . . . . . . . .
6.1.8.4. Lamination . . . . . . . . . . . . . . .
6.1.9. Fiberglass Forming . . . . . . . . . .
6.2. Annealing . . . . . . . . . . . . . . . .
6.3. Secondary or Finishing Opera-
tions . . . . . . . . . . . . . . . . . . .
6.3.1. Cutting . . . . . . . . . . . . . . . . . .
6.3.2. Grinding . . . . . . . . . . . . . . . . .
6.3.3. Polishing . . . . . . . . . . . . . . . . .
6.3.4. Heat Processing . . . . . . . . . . . .
6.3.5. Sintering . . . . . . . . . . . . . . . . .
6.3.6. Chemical Treatment . . . . . . . . . .
6.3.7. Surface Coating . . . . . . . . . . . .
7. Uses . . . . . . . . . . . . . . . . . . .
7.1. Silica and Silica-like Glass . . . . .
1. Definition and Historical
Summary
Many molten materials do not crystallize to
their parent crystalline phases once the thermo-
dynamic melting temperature T m is passed on
cooling. Such melts easily supercool to a temper-
ature far below T m and congeal to solids without
any attendant discontinuous changes in volume
or entropy. These solids, which are isotropic in
all their properties, are known as glass.
A common misconception is that all glass has
the same composition. A variety of organic and
inorganic materials can form glass, and most of
those that do exhibit a moderately sharp transi-
tion into the glassy state from the liquid. Most
common inorganic glass-forming systems are
covalent compounds of the following elements:
Si, B, Ge, Sn, Pb;
P, As, Sb;
O, S, Se, Te.
Some elements (e.g., Se, Te, and S) also read-
ily form glasses.
The canonical definition of the term glass is
that by Morey [54]: “Glass is an inorganic sub-
stance in a condition which is continuous with,
and analogous to, the liquid state of that sub-
stance but which, as the result of a reversible
change in viscosity during cooling, has attained
so high a degree of viscosity as to be, for all
practical purposes, rigid.” Similarly, the ASTM
defines glass as “an inorganic product of fusion
that has cooled to a rigid condition without crys-
tallizing.”
77 7.2. Flat Glass . . . . . . . . . . . . . . . . 82
77 7.2.1. Reflective Glass . . . . . . . . . . . . 82
77 7.2.2. Laminated Glass . . . . . . . . . . . . 82
78 7.2.3. Solar Glass . . . . . . . . . . . . . . . 82
7.3. Laboratory Glassware . . . . . . . 82
78 7.4. Light-Sensitive Glass . . . . . . . . 83
78 7.4.1. Photosensitive Glass . . . . . . . . . 83
78 7.4.2. Photochromic Glass . . . . . . . . . . 83
79 7.5. Display Devices . . . . . . . . . . . . 83
79 7.6. Glass Fibers . . . . . . . . . . . . . . 84
79 7.7. Molded Optics . . . . . . . . . . . . . 84
80 7.8. Glasses for Nonlinear Optical De-
80 vices . . . . . . . . . . . . . . . . . . . 84
81 8. Economic Aspects . . . . . . . . . . 84
81 9. References . . . . . . . . . . . . . . . 86
Ease of glass formation is almost entirely a
kinetic question. At no temperature is glass an
equilibrium phase, although glasses hundreds of
millions of years old are not uncommon in na-
ture. The cooling rate required to form a glass
varies with composition. Some melts (e.g., those
of SiO2 or B2 O3 ) can form a glass at very slow
rates of cooling, whereas mixed nitrates of potas-
sium and calcium or sulfates of potassium and
zinc, for instance, require rapid cooling from
their normal melting temperature to form glass.
Glassy metals have become quite common with
the advent of rapid (splat) cooling techniques,
the easiest to form having the approximate for-
mula Mx Ly , where M is a transition metal; L
is Si, P, C, B, or Ge; x = 0.7 – 0.8; and y = 0.3 –
0.2 (see → Metallic Glasses). Glasses can even
be made from melts of metals such as iron and
cobalt, but still higher quench rates are required
than those for metal – metalloid glasses. Almost
any inorganic melt can apparently be quenched
into a glass with a sufficiently fast quenching
rate.
Glass is not merely a supercooled liquid. The
distinction between a supercooled liquid and a
glass lies in the ability of structural elements
in the former to rearrange themselves in accor-
dance with the thermodynamic state of the sys-
tem, whereas in the latter such rearrangement is
not possible. This inhibition of rearrangement in
glass is caused by the large increase in viscos-
ity on cooling and gives rise to an endothermic
effect on heating, which occurs at the glass tran-
sition temperature (i.e., the temperature above
which structural elements in the glass are suffi-

ciently mobile to rearrange themselves accord-
ing to their equilibrium configuration).
Literature on glass is abundant. The structure
and content of this article are based on ency-
clopedia articles by Gliemeroth and Müller
[1] and by Boyd and Thompson [2]. Books
on the scientific and manufacturing aspects of
glass are the ones by Balta and Balta (1976)
[3], Dunken (1981) [4], Frischat (1975) [5],
McLellan and Shand (1984) [6], Paul (1982)
[7], Trier (1987) [8], Turkdogan (1983) [9],
Vogel (1985) [10], the Proceedings of the Con-
ferences on Glass Problems edited by Drum-
mond (1986) [11], the Proceedings of the First
International Conference on Advances in the Fu-
sion of Glass edited by Bickford et al. [12] and
the ones edited by Boyd and McDowell (1986)
[13], Tooley (1974) [14], and Giegerich and
Trier (1969) [15], [16]. The last book, though
fairly old, is still the standard work on all glass-
forming machines except for float glass; the pri-
mary difference between then and now being the
optimization of economic performance of glass
machines. A fairly extensive review of the spec-
troscopic properties of glasses is found in Wong
and Angell (1976) [17]. A review of the spec-
troscopic techniques of choice for silicates can
be found in the book edited by Hawthorne
(1988) [18]. For the physics of silica the book
edited by Pantelides (1978) is still the primary
source [19]; for the chemistry of silicon the book
by Iler (1979) [20] and the one edited by Corey
et al. (1988) [21]. Among the literature on col-
ors in glasses and minerals the books by Weyl
(1961) [22], Burns (1970) [23], Bramford
(1977) [24] and Nassau (1983) [25] and the ar-
ticles by Fritsch and Rossman (1987, 1988)
[26] – [28] and Schreurs and Brill (1984) [29]
should be consulted. The older literature on
glasses is extensive and includes a review ar-
ticle by Kauzmann (1948) [30] and Uhlmann
(1983) [31], and books by Ubbe-lohde (1965)
[32] and Rawson (1966) [33]. Pertinent classi-
cal references are the works by Morey (1938)
[34], Tamman (1925) [35], and Weyl and Mar-
boe (1962 –1964) [36]. Some sense of develop-
ments in the physics of amorphous materials, in-
cluding spin glasses, and attempts to grasp their
character in terms of localization and percola-
tion can be gleaned from the thirty-first session
on ill-condensed matter at Les Houches edited
by Balian et al. (1978) [37]. Compilations of
Glass 3
glass systems are found in the Phase Diagrams
for Ceramists vol. I – V (1973 – 1985) [38] and
in Mazurin’s books on phase diagrams (1973 –
1980) [39] and glass properties (1983 – 1987)
[40]. Physical properties of glasses can be found
in handbooks written by Bansal and Dore-
mus (1986) [41], Carmichael (1982) [42], and
Clark (1966) [43]. Barin and Knacke (1973)
[44], Chase et al. (1985) [45], Kubachewski
and Evans (1958) [46], and Robie et al. (1979)
[47] provide a wealth of thermodynamic data
on silicate systems as does the definitive book
on the structure of silicates by Liebau (1985)
[48]. Phosphate mineralogy is covered in the
book by Nriagu and Moore (1984) [49], its
chemistry by Van Wazer (1958) [50]. The Slag
Atlas (1981) [51] gives a fairly extensive compi-
lation of properties as well as an excellent syn-
opsis of all property measurement techniques
for glass systems of interest to the welding and
metal industry. Two more books on glass are the
ones edited by Lewis (1981) [52] and Mazurin
(1989) [53].
The discoverer of glass manufacture will
probably remain unknown. A source of inspi-
ration may have been the abundant occurrence
of glasses in nature. Obsidian, pumice (a natural
foam glass), and tektites (glassy bodies proba-
bly of meteoric origin) are examples of naturally
occurring glass. The earliest tektites worked by
humans date from the Magdalenian period about
25 000 years ago. A synopsis of the developmen-
tal history of glass follows.
b.c.
∼2000 Glass was manufactured in the Cauca-
sus.
∼1500 Small artifacts were made in Atchana,
Alalakh, and Tell al Rimah.
∼1480 In what was probably the first occur-
rence of glass in Egypt (Thutmose III:
Amarna period), alkali silicate glasses
were colored with CaO, Pb2 Sb2 O7 ,
Al2 O3 ; chromophores were Cu, Fe,
and Mn. Asian glassmakers settled in
Egypt.
∼1450 Beautiful glass vases were made, inlaid
with multicolored filigree glass.
∼1200 Glass technology declined in Asia mi-
nor (Egypt, Mesopotamia).
∼900 New glass centers started on the coast
of Syria and in Mesopotamia.
4 Glass
∼700 – 600 Glass making was established on
Rhodes and Cyprus.
∼630 Clay tablets in the Sardanapal library in
Assyria describe use of tin as opacifier,
production of alkali from plants, manu-
facture of frits and colorants.
∼500 First Chinese glass artifacts date from
this period.
∼332 Alexander the Great supported ex-
pansion of Syrian technology.
∼250 The blowpipe was discovered.
a.d.
Torso of an Aphrodite from Alexandria,
cut from green glass, dates from this
time.
First glass retorts were made for al-
chemists.
∼70 Glassworks were constructed in Spain
and France (glass manufacture was im-
ported by the Romans from Egypt).
79 Pliny described the manufacture of
glass.
100 Glass was manufactured in Köln.
100 Glass vessels were sold in Syrian shops
in Sidon.
First vessels with relief were blown in
molds.
300 Late Roman glass art from this time has
been found in Christian catacombs.
∼500 Syrian glass shops manufactured ves-
sels with glass filament supports, head
vessels with cut and etched patterns.
591 Gregory of Tours mentioned glass
church windows.
674 Glass windows were used in English
churches.
∼700 Window glass was manufactured in
Syria by blowing, cutting, and sagging.
∼700 Alkali content was lowered with respect
to P2 O5 (in bone ash).
∼1000 Glass windows were made for Te-
gernsee cloister.
∼1100 Small hand-held bend mirrors were in-
troduced.
1180 Glass windows were first used in private
English houses.
1202 Zenith of melt painting with copper
containing colored glasses in the mid-
dle Rhine region.
∼1300 Glass windows became more common
in Europe.
1405 Silver engravings with glass layers were
produced in Italy.
1453 Glass-making knowledge moved from
Byzantium to Venice.
∼1500 Clear glass was manufactured by glass
shops in Murano, particularly wine
glasses exported to Germany. Glass
was decorated with pearls and buttons,
painted, and gold plated.
∼1500 Diamond was used to cut glass.
1507 Orlando Gallo improved Venetian
glass technology. Mirrors were pro-
duced. Zenith of Venetian glass manu-
facture occurred.
∼1550 Late blooming of Gothic glass painting
appeared in Chartres and Paris.
1550 Glass thermometer was manufactured
in Venice.
1590 Lenses were produced, presumably by
Zacharias Janssen.
1665 Large mirrors were made in France.
1680 Johan Kunkel (1630 – 1702) manu-
factured ruby glass.
1688 Mirror glass was poured.
1697 Bohemian glass was produced in
Venice.
1728 Reamur observed devitrification.
1754 Klingenstjerna disproved the thesis
of Newton that refractive index is in-
dependent of wavelength.
1757 Dellond constructed achromatic ob-
jective lenses.
1782 Industrial temperature measurement
became possible with the Wedgwood
pyrometer.
∼1800 The first attempts were made to under-
stand the constitution of glass.
1834 Leng interpreted devitrification as
crystallization of silicic acid salts.
1845 Pocket watch industry started in a glass
shop.
1857 The first glass oven with regenerative
heating was developed.
1859 Semiautomatic bottle-blowing machine
was used.
1867 Continuous tank was introduced.
1869 Silica was first drawn.
1879 The first blanks for incandescent lamps
were made.
1900 Cylindrical blow machines were used
for window manufacture.

1903 Owens invented suction machine for
bottle manufacture.
1904 The first neon light fixtures were made.
1906 Fourcault developed sheet-draw ma-
chine.
1909 A 1.52-m telescope mirror was manu-
factured for Mount Wilson observatory.
1915 Pyrex was introduced.
1917 Tank-drawn sheet glass appeared (Col-
burn machine).
1922 Single gob feeder was developed.
1925 Pittsburgh process for sheet glass was
introduced.
1925 Draw process was used for tubes.
1926 Ribbon machine was developed for in-
candescent lamp bulb blanks.
1934 World’s largest piece of glass was cast
for 200-inch (5.08-m) telescope mirror
on Mount Palomar, California.
1949 Centrifugal casting of television tubes
began.
1950 First photosensitive glasses were made.
1967 Floating glass process was invented by
Pilkington.
1970 Optical fibers were demonstrated with
20-dB/km loss.
1972 Vertical melting units were developed.
1978 Polychromatic glass was invented.
∼1980 Development of fluoride-based glasses
for optical fibers.
1983 Sol – gel extruded mullite fiber was in-
vented.
1984 Pressing of elongated automobile head-
lights.
2. Structure of Glass
Methodology in condensed-matter physics and
chemistry consists of identifying and relating the
physical properties, structure, and constituent el-
ements of a class of materials. For crystalline
solids, the constituents and structure can be char-
acterized readily. In glass, on the other hand, un-
derstanding of the structure consists almost ex-
clusively of negative statements: no metric ge-
ometry, trivial space group, no Bloch states, no
single ground state, no unique best structure. In
addition, the topology of glass structure is almost
amenable only to indirect experimental investi-
gation.
Glass 5
It is not surprising in light of the undeter-
mined nature of the amorphous state of glass
that competing perceptions exist with regard to
its character. The principal difficulty in distin-
guishing between models has been the small
amount of energy associated with long-range
ordering. For instance, the enthalpy of for-
mation of quartz from silicon and oxygen at
298 K is − 860 kJ/mol; this is only 12 kJ/mol
more negative than that for vitreous fused sil-
ica (− 848 kJ/mol). Only 1 % of the enthalpy
of formation of quartz is therefore associated
with long-range ordering. The two predominant
structural models for glass are the microcrystal-
lite and the random network hypotheses.
Microcrystallite Hypothesis. The micro-
crystallite “cybotactic group” hypothesis was
constructed primarily to account for the dis-
continuous changes in the properties of glasses
which can be correlated with similar disconti-
nuities in the properties of associated crystalline
phases. Proponents of this hypothesis were (with
some rare exceptions such as Stewart and
Randall [55], almost exclusively Russian, the
first being Frankenheim (1835)
and subsequently von Weimarn (1907)
who held that all matter in any state, be that gas,
liquid, or solid is crystalline [56]. This work was
followed up by Lebedeff (1921), who showed
that vitreous amorphous silica varies consider-
ably between 540 and 600◦ C in its double re-
fraction, refractive index, and coefficient of ex-
pansion [57]. He inferred that this variation was
due to a polymorphic transformation assumed
to be connected with the low – high tempera-
ture transformation of quartz, which occurs at
575◦ C. He furthermore suggested that vitreous
silica consists of an aggregate of very minute
crystals with included quartz crystals that are
probably not in a pure state, but in the form of a
solid solution with other substances, hence ac-
counting for the temperature range over which
the polymorphic transition occurs. Valenkov
and Poray-Koshitz (1936) analyzed the X-ray
diffraction curves of glasses and concluded that
the observed diffraction patterns [58] were pro-
duced by 0.75 – 2.5-nm crystallites that were
connected to each other by an amorphous layer.
These results made the microcrystallite postu-
late questionable because 2.5-nm crystallites
do not represent long-range ordering in a crys-
6 Glass
tallographic sense. Refinement of diffraction
experiments, particularly at small angles, has
invalidated the original microcrystallite hypoth-
esis. Recent electron microscopy results, on
the other hand, indicate that multicomponent
glasses can be chemically inhomogeneous, and
contain microheterogeneities which could be
taken to represent microcrystallites.
Random Network Hypothesis. The
Zernike –Prins – Bernal – Fowler – Warren hy-
pothesis [55] considers the liquid a system of
atomic or ionic networks, designated as a ran-
dom network. For glasses this implies a rigid
system of continuous noncrystalline networks
similar to those assumed to be present in the
liquid. It remains open to debate whether there
is one unique random network or perhaps more
than ten thousand or what random really means
in the context of liquid structures. The hypoth-
esis was successful in providing qualitative ex-
planations for the glass-forming tendency of
simple glass-forming systems as being caused
by a rapid increase in viscosity during cooling
of the melt. In addition successful predictions
could be made about potential glass-forming
systems as well as rationalizations for most of
property-composition relationships. Zachari-
asen (1933) postulated glass-forming tenden-
cies for simple oxides based on random net-
works and the concomitant need for flexibil-
ity in linkages [59]. These postulates, in part
already phrased by Goldschmidt (1926) for
onide glasses [60], are the following:
1) Each oxygen atom can be linked to no more
than two cations; the number of oxygen
atoms around any one cation must be small,
i.e., three or four; the oxygen polyhedra must
share corners, not edges or faces, to form a
three-dimensional network; at least three cor-
ners must be shared.
2) Network formers have a coordination num-
ber of 3 or 4 (Si, B, P, Ge, As, Be, etc.);
network modifiers have coordination num-
bers greater than or equal to 6 (Na, K, Ca,
Ba, etc.). Intermediate atoms with a variable
coordination number between 4 and 6 (Li,
Al, Mg, Zn, Pb, Nb, Ta, etc.) can function as
network modifiers as well as network form-
ers; the coordination change is a reflection of
their amphoteric character, i.e., solubility in
both inorganic acids and bases.
Additional refinements have been made to
the random network theory. Dietzel (1942) in-
troduced the concept of cationic field strength
defined as formal cation charge divided by the
cation – anion distance [61]. This concept en-
ables a quantifiable distinction to be made bet-
ween the three categories of atoms:
1) network formers with a field strength of 1.4 –
2 N/m,
2) network modifiers with a field strength of
0.1 – 0.4 N/m, and
3) amphoteric atoms with a field strength of
0.5 – 1.0 N/m.
Glass formation is favored if the difference in
field strength between the cations is larger than
0.3. Smekal (1949) expanded on the cationic
field strength concept by taking the bond po-
larity into account [62]. Glass formation is fa-
vored if mixed bonding with a homopolar and
heteropolar component occurs. Weyl (1958 –
1959) postulated the screening theory used to ex-
plain the mechanical properties of glasses [63].
In this theory the polymerization of polyhedra
to threedimensional random networks is caused
by the polarization and deformation of residual
valence forces. Stevels (1948) developed a the-
ory for invert glasses, which contain polyhedra
with less than three connected corners in contra-
diction to the Zachariassen postulates [64]. His
structural parameter Y is a measure of the aver-
age number of bridging anions. The properties of
the glass are mainly determined by the network
modifier atoms when Y is smaller than 2. This
is due to the fact that these network modifiers
compete for the available anions, thus resulting
in an increased degree of disorder.
Among the less fruitful extensions of the ran-
dom network theory are those by Huggins and
Tilton. Huggins (1955) attempted to explain
known discontinuities in properties by assuming
the presence of fixed atom groups, called struc-
tons [65]. A last refinement of the network hy-
pothesis represents the work by Tilton (1957),
who postulated the presence of vitrons: aggre-
gates of silica tetrahedra primarily consisting of
five-membered rings, which combined to form
a pentagondodecahedron consisting of 20 tetra-
hedra [66]. These vitrons would be connected to
one another by less ordered domains.

With the advent of NMR, laser Raman spec-
troscopy, and extended X-ray absorption fine
structure (EXAFS), focus has been directed to
dissecting glass structure in terms of local envi-
ronments, avoiding any deterministic statements
regarding extended structures. An area of re-
search involves determining the extent to which
long-range structural elements can be derived
from such local environments.
2.1. Structure of Special Melts and
Glasses
Almost all industrially manufactured glasses are
silicate glasses. As a consequence, these sys-
tems are emphasized in the following discus-
sion, the goal being to provide a terminus a quo
rather than a terminus ad quem for the study
of amorphous materials. The viscosity of var-
ious silica-containing melts is used as a ref-
erence against which structural concepts can
be matched. The use of viscosity is somewhat
ironic, however; although viscosity illustrates
nicely the role of network-forming atoms in
comparison with network-modifying atoms, it is
the least understood property of melts or glasses.
The structural description of glasses and melts
is based on Q (quartz) distribution theory and
Q designation. The use of this model enables
description of silica species in both solids and
aqueous solutions in terms of the distribution of
local silicon environments, which are amenable
to investigation by NMR. These designations are
as follows (Fig. 1):
1) Each silicon atom is coordinated tetrahe-
drally to four oxygen atoms.
2) If all oxygen atoms in a tetrahedron are con-
nected to two silicon atoms, the local envi-
ronment around the silicon atom is desig-
nated Q4 . All four Si−O bonds of the tetra-
hedron are, therefore, bridging bonds, desig-
nated Si−O(br).
3) The local silicon environments are desig-
nated Q3 , Q2 , Q1 , and Q0 if three, two, one,
or zero oxygen atoms are connected to two
silicon atoms. In Q3 , three Si−O(br) bonds
and one Si−O nonbridging bond, designated
Si−O(nbr) exist. For Q0 , all Si−O bonds are
Si−O(nbr).
Glass 7
4) Designations Q4 to Q0 of local environments
coincide with connectivity 4 to connectivity
0 of the extended environment.
Four reactions suffice to describe all possible
rearrangements in local environments in those
alkali oxide (R2 O) silicate glasses in which all
oxygen atoms are connected to silicon atoms
[69]:
1) 2 Q4 + R2 O
2 Q3 (depolymerization)
2) 2 Q3
Q2 + Q4
3) Q2 + Q3
Q1 + Q4 (stepwise condensation)
4) Q1 + Q3
Q0 + Q4
The Q distribution can in principle be deter-
mined experimentally by high-resolution solid-
state NMR. This distribution does not, how-
ever, necessarily relate glass structure to glass
properties. Examination of Figure 2 makes this
clear. Two hypothetical two-dimensional net-
works, each containing 45 open tetrahedra and
11 black tetrahedra, are shown. The open tetra-
hedra represent silicon; the black tetrahedra,
lithium in fourfold oxygen coordination. The
difference in Q distribution between the two
networks is small. Nevertheless, measurement
of the transport properties of the two networks
would give wildly different results; the arrange-
ment in Figure 2B has very high electrical con-
ductivity and diffusivity (and possibly low vis-
cosity) because of a continuous pathway through
the solid in contrast to that in Figure 2A. Clearly
the Q distribution does not correlate glass struc-
ture with glass properties and additional infor-
mation is required to make such a connection.
This additional information is obtained from
Monte Carlo type computer calculations.
Keefer [70] recognized that the question of
the structure of a silica-rich alkali-metal silicate
glass is analogous to that of electron spin cor-
relation in a two-dimensional Ising model. This
model attempts to explain magnetic properties
of materials by constructing a lattice with two
possible electron spin states, up or down, which
allows the problem to be considered in terms of
a statistical distribution. Alkali silicate and spin
glasses share two characteristics: (1) slow relax-
ation and (2) a tendency to settle into any one of a
large number of atomic configurations. In silica-
rich alkali-metal silicate glasses, the two possi-
ble spin states correspond to bridging and non-
bridging oxygen atoms; silica-rich glass is re-
quired because photoelectron spectroscopy has
8 Glass
demonstrated that only in such systems are non-
bonding oxygen atoms not present. In the ab-
sence of nonbonding oxygen, the ratio between
bridging and nonbridging oxygen atoms is fixed
by the stoichiometry of the sample.
Figure 1. Structure and designation of silica species; possi-
ble number of local environments around a silicon atom up
to the third-nearest neighbor [67], [68]
As stated before, connecting Q distribution
with physical properties of a glass or melt re-
quires Monte Carlo type calculations. The com-
putational problem involves assignment of the
enthalpies of formation of the four principal re-
actions between Q species; calculation of net-
work patterns; derivation of the thermodynamic
properties of the system from these patterns; and
use of percolation theory to compute the rheo-
logical and transport properties of melts [72]. A
rule of thumb is given by Ziman with respect
to site percolation [73]: site percolation occurs
in a regular three-dimensional assembly when
favorable regions occupy ca. 15 % (in the two-
dimensional case 45 %) of the total volume.
Figure 2. Two-dimensional nets of silica tetrahedra () in-
terspersed with lithium tetrahedra (
)
A) 36 Q3 , 9 Q2 ; B) 33 Q3 , 13 Q2 Courtesy of J. Dickinson,
Corning Incorporated
Local silicon environments can be measured
by 29 Si magic angle spinning (MAS) NMR. Two
problems arise in using this technique: variations
in chemical shift for a specific silicon species
and, partly as a result of this, limited spectral

resolution. The first problem is illustrated in Fig-
ure 3, which shows the 29 Si MAS NMR spec-
trum of Na24 Y8 [Si24 O72 ], which is a single-
chain silicate with 24 silica tetrahedra per unit
cell (a 24er chain in the Liebau classification)
and local environment Q2 . The 29 Si MAS NMR
spectrum of this compound shows 12 peaks with
a chemical shift range of 5.12 ppm. Thus, small
perturbations in the local environment around
one Q2 species can cause a substantial chemi-
cal shift. In this case, the variations are due to
chain twisting [71]. Such variations in chemical
shift of a single silica species, combined with the
large number of species possibly present (ten Q2
species are possible) and the limited NMR spec-
tral resolution in glass, render determination of
the silica species distribution in glass tentative at
best. Despite this, some assessment of the degree
of intermediate-range order in lithium silicate
glasses has been obtained by combining NMR
and ESCA (electron spin chemical analysis) re-
sults together with the application of proper stoi-
chiometric constraints on the system [69]. Doing
this shows clearly that the 29 Si NMR spectra of
such glasses indicate the presence of only a small
number of local environments, in contrast to the
total possible number enumerated in Figure 1.
Figure 3. The 29 Si MAS NMR spectrum of
Na24 Y8 [Si24 O72 ]
δ (ppm) =−26.793 – 0.4255 θwhere δ is the chemical shift
and θ the Si – O – Si angle.
Glass 9
2.2. Composition of Glass
Multicomponent glass-forming systems con-
tain, according to Zachariasen, appreciable
amounts of elements that form vitreous oxides
or other elements that can replace the former
isomorphously. Ternary glasses can consist of
one network former and two modifiers, two net-
work formers and one modifier, or three network
formers. Most ternary oxide systems have been
sampled, and investigation has been extended to
quaternary and quinary systems.
The properties of complex industrial glasses
tend to be rationalized in terms of simple
systems. The following discussion, therefore,
begins with vitreous silica as the canonical
single-component glass, followed by simple
two-component systems: the alkali-metal and
alkaline-earth silicate, borate, phosphate, and
germanate glasses. Boro-, alumino-, and lead
silicate glass is then discussed, followed by two
nonoxide systems, the chalcogenide and halide
glasses. Finally, the chemical composition of in-
dustrially important glasses is tabulated.
2.2.1. Single-Component Glass
The most important single-component glass is
vitreous silica. The structure consists of corner-
sharing SiO4 tetrahedra. Each oxygen atom is
shared by two silicon atoms, forming Q4 lo-
cal silicon environments. Long-range order is,
of course, absent. Vitreous silica is an excellent
dielectric with a very low equilibrium solubility
(on the order of 100 ppm at room temperature)
in all acids except hydrofluoric. A synopsis of
the properties of Corning 7940 fused silica and
other amorphous silicas is given in Table 1.
The difference in structure between vitreous
silica and two crystalline silicas is shown in Fig-
ure 4. Here the frequency of occurrence of aver-
age Si−O−Si angles is illustrated by using the
29
Si MAS NMR spectrum of vitreous silica [76]
and the formula of Thomas and coworkers [77],
which relates chemical shift to the Si−O−Si
angle. Average Si−O−Si angles vary between
122◦ and 170◦ in vitreous silica, the most com-
mon value being 147◦ (or 151◦ if the spectrum
of Gladden and coworkers is used [78]). On
the other hand, quartz and cristobalite each have
10 Glass
Table 1. Properties of Corning 7940 fused silica and low-water (<100 ppm) vitreous silica [74], [75]

Softening point, K 1853

Annealing point, K 1357
Strain point, K 1229
Thermal expansion coefficient (273 – 573 K), 5.5×10−7
K−1
Density, g/cm 2.20
Refractive index 1.459
Log volume resistivity
523 K 11.8
623 K 10.2
Dielectric constant 3.8
Loss tangent (1 MHZ, 293 K), % 0.001
SiO vapor pressure over SiO2 , kPa

4
1000 – 3000 K (vacuum) logp (SiO) = 101.3 11.37− 2.7117×10
T

4

1000 – 3000 K (20.3 kPa partial oxygen logp (SiO) = 101.3 12.92− 4.066×10
T
pressure)
Maximum crystallization rate of cristobalite from
vitreous
silica (1948 K), cm/sec 2×10−7
Surface tension (calculated), N/m
298 K 5.200
2073 K 0.3
1149 – 2341 K σ = 0.236 212 + 3.25 × 10−5 T
Thermal conductivity (298 K), W m−1 K−1 1.37      ∗
Heat capacity (298 – 1500 K), J mol−1 K−1 74.369− 7.2594 × 10−3 T + 5.5704 × 10−6 T 2 − 3.114 × 10−6 T −2
Heat of formation (298 K), kJ/mol −903.2
Free energy of formation (298 K), kJ/mol −850.559
Entropy of formation (298 K), J mol−1 K−1 47.40
Heat capacity (298 K), J mol−1 K−1 37.94  
Viscosity (1873 – 2773 K), 0.1 Pa · s logη = −6.24+ 2.69 × 104 /T
Young’s modulus, GPa 72.9
Shear modulus, GPa 31.3
Poisson ratio 0.165
pH at point of zero charge 2

∗ Data for vitreous silica.

one single Si−O−Si angle, with values of 143◦
and 146◦ , respectively.
Superimposed on the plot of Si−O−Si angle
versus frequency in Figure 4 is the two-center
energy, taken to reflect the bond energy, for a
silicon – oxygen bridging bond as a function of
Si−O−Si angle, calculated by using semiempir-
ical molecular orbital calculations [79]. Inspec-
tion of this curve shows that a Si−O bond with
a Si−O−Si angle of 180◦ is stronger (i.e., has a
more negative two-center energy, ca. − 1760 kJ)
than that at a Si−O−Si angle of 120◦ (two-
center energy, ca. − 1530 kJ). Examination of
Figure 4 suggests that although glasses are in-
trinsically less stable than their crystalline coun-
terparts, a vitreous silica more stable than quartz
or cristobalite is conceivable; the challenge is
to make a glass with a larger percentage of
Si−O−Si angles >150◦ . Only this angle must
be considered because the energy barrier to rota-
tion between connected silica tetrahedra is neg-
ligibly small.
Fused silica transmits light of wavelengths
into the UV region and is the oxide glass most
resistant to damage caused by radiation. It finds
use in windows for space vehicles and wind tun-
nels, ultrasonic delay lines, crucibles for grow-
ing ultrapure silicon or germanium crystals, op-
tical fibers, and optical systems in spectropho-
tometric equipment.
Vitreous silica can be produced by several
methods. These processes and the impurities as-
sociated with them are listed in Table 2.
Fused quartz made by electrically fusing
quartz crystals has very low moisture content
and, hence, good IR transmission for wave-
lengths < 4500 nm. The disadvantage of quartz
as a raw material is that even high-grade pure
 Glass 11
Table 2. Continued
quartz crystals contain 1 – 2 ppm of aluminum,
alkali, manganese, and titanium. The presence Fusion of quartz oxides 110 ppm Ge 204 A
of these elements increases the number of (max.)
Si−O(nbr) bonds, which thereby reduces UV Al2 O3 52
CaO 23
transmission for wavelength < 4500 nm. Flame water free
fusion of quartz or flame hydrolysis of SiCl4 , on Soot deposition on Al <0.02 Corning 7943
the other hand, gives glasses of very high purity Pt mandrel by Ca <0.1
except for large amounts of water, which de- SiCl4 flame Fe <0.1
hydrolysis;
crease IR transmission. For some applications, fired on Na <0.04
impurities as low as 1 part in 1012 become im- graphite mandrel OH 10
portant. An example is uranium; this problem in H2
Flame hydrolysis OH 1000 Corning 7940
is best solved by ensuring that the silica source of SiCl4
is biogenic rather than associated with granitic Vacuum fusion Al2 O3 100
rocks or pegmatites. of sintered Na2 O <200
Cab – O – Sil. OH 2000
Table 2. Impurity levels in various grades of fused silica powder

Production method Impurity, ppm Trade name

Flame fusion Al 10
of quartz B <0.5 OG, OH Vitreosil
(Thermal Syndicate),
Herosil, Homosil,
Vitrasil (Heraeus)
Ca 0.35
Fe 0.51
Na 0.06
OH 400
Electric fusion Al 50 IR Vitreosil
(Thermal, Syndicate),
Infrasil (Heraeus),
Pursil (Quartz et
Silice)
of quartz Sb 0.23
B <0.5
Ca 0.4
Fe 0.74
Na 4.0
OH 3.0
Vapor-phase Al <0.02 Spectrosil (Thermal
hydrolysis Syndicate), Suprasil
(Heraeus), Tetrasil Figure 4. Difference in structure between vitreous silica and
(Quartz et Silice) two crystalline silicas
in flame: Ca <0.1 a) Frequency of occurrence of average Si−O−Si angles
SiCl4 −→ SiO2 Fe <0.1 in vitreous silica; b) Si−O bond energy as a function of
Na <0.04 Si−O−Si angle
OH 1200 Si – O – Si angle: Quartz 143.6◦ ; Cristobalite 146.4◦ ; Co-
High-temperature Al <0.02 Spectrosil WF esite 144.2◦ , 152.8◦ ; Tridymite 146.7 – 157.2◦ .
(Thermal Syndicate),
Suprasil I (Heraeus)
vapor-phase Ca <0.1
oxidation: Fe <0.1
SiCl4 −→ SiO2 Na <0.04
2.2.2. Silicate Glasses with Two Components
OH 3
Cl 500 Two-component silicate glasses are of particu-
Fusion of quartz oxides 260 ppm Ge 201 lar interest in studying glass formation. Addition
(max.) of alkali-metal or alkaline-earth oxides breaks
Al2 O3 180
water free
Si−O−Si linkages, the alkali-metal or alkaline-
earth nestling at nonbridging oxygen sites in the
network, hence, the description network modi-
fiers. This decrease in connectivity of the silica
network manifests itself in a very large decrease
12 Glass
Table 3. Viscosity and other properties of alkali-metal (R2 O) and alkaline-earth (RO) silicates and silica [63], [80], [81]

Composition, mol % CAS registry no. Cationic field force, 1015 Single bond energy, Viscosity, Pa · s a
R2 O or RO N/m2 kJ/mol [82]
0 (100 % SiO2 ) [10097-28-6] 1.57 463 1.47×104 b
2.40×103 c
Li2 O [12057-24-8] 0.23 150
20.0 19.1
25.0 8.1
30.0 2.8
35.0 1.4
40.0 1.0
Na2 O [1313-59-3] 0.19 84
15.0 50.1
20.0 15.8
25.0 7.9
30.0 4.5
35.0 2.5
40.0 1.4
K2 O [12136-45-7] 0.13 54
16.9 35.5
20.0 27.0
22.3 22.9
25.7 11.5
37.0 6.0
Rb2 O [18088-11-4] 0.12 50
20.0 56.5
25.0 28.3
33.3 9.3
Cs2 O [20281-00-9] 0.10 42
20.0 100.0
25.0 39.9
33.3 10.0
MgO [1309-48-4] 0.45 155
44.3 0.46 d
45.8 0.26 d
51.3 0.15 d
CaO [1305-78-8] 0.33 134
43.7 0.24
48.7 0.15
52.7 0.10
SrO [1314-11-0] 0.27 134
40.5 0.48
44.3 0.28
50.9 0.20
BaO [1304-28-5] 0.24 138
40.2 0.54
42.1 0.33
49.8 0.19
a
1673 K for R2 O and 1973 K for RO compositions, respectively.
b
2197 K.
c
2333 K.
d
Extrapolated.

in viscosity (see Table 3), melting point, and UV
transmission. Modifiers also cause a decrease in
resistivity, an increase in thermal expansion, and
generally lower chemical durability.
Different alkali-metal atoms have different
effects on the properties of silicate glasses.
Thus, lithium silicate glasses are nonhygro-
scopic, whereas sodium, potassium, rubidium,
or cesium silicate glasses show increasingly
higher hygroscopicity. Another example is the
volume contraction of the silicate network in the
presence of lithium and its expansion in the pres-
ence of potassium. The almost monotonic varia-
tion in cation – oxygen distance, as measured by

Figure 5. Freezing point depression for alkali-metal sili-
cate melts (10 R2 O · 90 SiO2 ) as a function of cationic field
strength
Figure 6. Surface tension of alkali-metal silicate melts
(20 R2 O · 80 SiO2 ) at 1673 K as a function of cationic field
strength
X-ray diffraction, has led to a variety of schemes
for the comprehensive compilation of the prop-
erties of alkali-metal or alkaline-earth silicate
crystals or glasses. Among these are the cation
field energy and field strength, which are the for-
mal cation charge divided by the cation – anion
Glass 13
Figure 7. Viscosity of 20 R2 O · 80 SiO2 melts at 1673 K as
a function of cationic field strength
Figure 8. 29 Si MAS NMR chemical shifts of 33 R2 O ·
67 SiO2 (R = alkali metal) crystalline silicates as a function
of cationic field strength of the alkali-metal atom
The observed chemical shifts relative to tetramethylsilane
(SiMe4 ) are − 93.3, − 95, − 101, and − 101.5 for crys-
talline lithium, sodium, potassium, and cesium disilicate re-
spectively
distance and the square of the cation – anion dis-
tance, respectively.
Many physical properties of alkali-metal or
alkaline-earth silicate glasses change almost
monotonically as a function of cationic field
strength or energy. For example, the critical
14 Glass
liquid immiscibility temperature decreases lin-
early as a function of cationic field strength
from magnesium to barium silicates, and from
lithium to cesium silicates. Similarly, the freez-
ing point depression increases more or less
monotonically from lithium to cesium silicates
(see Fig. 5), whereas the surface tension de-
creases (see Fig. 6). Viscosity, refractive index,
and density (see Fig. 7) show a minimum for
sodium silicate melts.
Even the few 29 Si MAS NMR chemical shift
data on crystalline alkali-metal silicates suggest
a relation between chemical shift and cationic
field strength, less negative (downfield) chemi-
cal shifts being associated with greater cationic
field strength (Fig. 8). More sophisticated anal-
ysis of a variety of silica-containing systems
has been carried out [83], [84]. In alkali-metal
or alkaline-earth silicate glasses, most physi-
cal properties vary more or less linearly with
cationic field strength, with the exception of vis-
cosity, refractive index, and density. Although it
is useful as a mnemonic device, no true cause
and effect relations are associated with cationic
field strength or energy.
Table 4. Viscosity of alkali borate glass (1173 K) [86]
R2 O, mol % Viscosity, Pa · s
0 (100 % B2 O3 ) 14.2
Li2 O
2.5 3.1
13.9 0.8
25.6 0.46
Na2 O
3.0 3.0
15.7 1.4
24.5 0.8
K2 O
2.1 3.7
15.9 1.5
23.5 1.0
2.2.3. Borate, Phosphate, and Germanate
Glasses
Borate glasses contain planar BO3 groups
as structural units, rather than tetrahedral SiO4
groups. The oxygen atoms are, as in silica, again
connected to two network-forming atoms, in
this case boron. Radial distribution analysis de-
scribes the B2 O3 glass structure as consisting of
boroxyl rings, i.e., planar rings containing three
boron atoms and three oxygen atoms. Molecular
dynamics have shown that the radial distribution
pattern is consistent with structures having a low
concentration of such rings [85].
Although borate glass forms a three-
dimensional network, its viscosity is substan-
tially lower than that of silicate glass, as shown in
Table 4. Again, addition of alkali lowers the vis-
cosity of the melt, but the effect is by no means
as dramatic as for silicate glass [86].
Introduction of alkali or moisture to alkali-
metal borate glasses causes some of the
three-coordinate boron atoms to become four-
coordinate, as shown by the pioneering NMR
work of Bray and O’Keefe [87], [88]. The ra-
tio of three- to four-coordinate boron in alkali-
metal borate glasses has an upper limit of about
1.2.
Figure 9. Oxygen 1 s photoelectron spectrum of 50 SrO ·
50 P2 O5 glass [88]
Solid lines indicate experimental data. Dashed lines indicate
analytical data.
a) Total spectrum; b) Nonbridging oxygen; c) Doubly
bonded oxygen (P = O); d) Bridging oxygen
Phosphate glasses contain tetrahedrally co-
ordinated PO4 building blocks; however, they do
not show the same type of connectivity as silicate
glasses. Oxygen 1 s photoelectron spectroscopy
suggests that in phosphate glasses, three types of
oxygen atoms occur: those bonded to two phos-
phorus atoms, the bridging oxygens O(br); those
bonded to one phosphorus atom and one alkali-
 Glass 15

metal atom, the nonbridging oxygens O(nbr); Oxygen 1 s photoelectron spectroscopy indi-
and those bonded only to phosphorus, the dou- cates both the concentration of different oxygen
bly bonded oxygens O(d). A characteristic oxy- atoms in a material and the actual charges on
gen 1 s photoelectron spectrum of a phosphate these atoms. The relation between energy shift
glass is shown in Figure 9. In contrast, sili- of the oxygen 1 s photoelectron spectral line
cate glasses never contain double-bonded oxy- and charge is shown in Figure 10. According
gen atoms and only rarely nonbonded oxygen, to this method, quartz, cristobalite, and vitreous
i.e., oxygen atoms not connected to at least one silica have an oxygen charge of −0.74. Oxy-
silicon atom. An example of the latter is glassy gen atoms with higher negative charge are en-
Pb2 SiO4 . countered, for example, in lead silicate glasses,
which show oxygen charge variations compara-
ble to those found for superconducting materi-
Table 5. Oxygen 1 s binding energies and oxygen charges for als. Some oxygen 1 s derived charges for var-
crystalline and amorphous oxides (glasses) ious compounds are compiled in Table 5 [90].
Compound Binding O charge
Assignment of charges is a partitioning problem
energy, eV without a unique solution.
Crystalline oxides Some special phosphate glasses show a con-
SiO2 (vitreous silica, quartz, 532.4 −0.74 nectivity of four, identical to that found in vit-
cristobalite)
reous silica. Examples are ZnP2 O6 and AlPO4
B 2 O3 532.3 −0.75
GeO2 531.4 −0.78 glasses.
Al2 O3 531.0 −0.81 The structure of alkali phosphate glasses is
BeO 530.8 −0.82 well known because these glasses, in contrast
ZnO 530.6 −0.83
Mg2 SiO4 530.6 −0.83
to alkali silicate glasses, either do not, or only
Nb2 O5 530.3 −0.85 at very small rates, repolymerize on dissolution
SnO2 530.2 −0.86 in aqueous solution. As a result, the length of
Cr2 O3 530.2 −0.86 the phosphate chains remains unchanged. The
TiO2 530.1 −0.87
As2 O3 530.1 −0.87 relative proportions of different chains in solu-
ZrO2 529.8 −0.88 tion, analyzed chromatographically, give a true
CuO 529.7 −0.89 measure of the distribution of extended envi-
Fe2 O3 529.7 −0.89
MgO 529.5 −0.90
ronments in phosphate glasses. The most com-
PbO 529.4 −0.91 mon chain length is three to four phosphorus
MnO 529.2 −0.93 atoms, with a maximum chain length of seven.
NiO 529.1 −0.94 No analogies between the distribution of struc-
CaO 528.5 −0.96
YBa2 Cu3 Ox 530.2 −0.86
tural elements in phosphate and silicate glasses
528.2 −0.99 exist. This is due to the limited cross-linking
Bi2 CaSr2 Cu2 O16− x 531.2 −0.79 and branching that occur in phosphate glasses
529.2 −0.93 in comparison to silicate glasses due to the pres-
Amorphous oxides (glasses)
33 CuO – 17 Fe2 O3 – 50 P2 O5 532.05 −0.75 ence of P=O bonds.
531.55 −0.77 Phosphate glasses tend to have low durability.
25 WO3 – 75 TeO2 530.90 −0.81 Despite this, important commercial applications
530.65 −0.78
15 BaO – 35 ZnO – 50 TeO2 530.30 −0.85
exist. One of these is associated with the sharper
529.65 −0.89 absorption bands of iron oxide in the ultravio-
20 Na2 O – 80 SiO2 531.90 −0.75 let and infrared in phosphate glasses compared
530.50 −0.84 with silicate glasses. Iron-containing phosphate
24 GeO2 – 76 SiO2 531.3 −0.79
34 PbO – 61 SiO2 – 2 K2 O – 2 Na2 O – 532.6 −0.70 glasses are, therefore, nearly transparent to vis-
As2 O3 ible light, enabling the manufacture of virtually
530.4 −0.85 clear heat-absorbing glasses containing several
percent iron oxide.
16 Glass

Table 6. Viscosity and density of alkali germanate glasses

R2 O, mol % Viscosity (1673 K), Density (1473 K),

Pa · s g/cm3
0 (100 % GeO2 ) 633.4 3.46
Li2 O
1.39 55.0
2.48 5.7
5.0 3.57
8.02 0.63
10.0 3.59
20.0 3.49
Na2 O
1.58 11.0
4.29 1.8
5.0 3.61
7.79 0.51
10.0 3.61
20.0 3.44
Figure 10. Oxygen charge derived from oxygen 1 s photo- K2 O
electron spectra [89] 0.84 31.9
4.58 1.4
Phosphate-based glasses are more resis- 5.0 3.56
tant than silicate glasses to hydrofluoric acid. 7.41 0.3
10.0 3.49
Some optical glasses produced by Schott, Hoya, 20.0 3.18
Owens-Illinois, and Corning France use phos-
phate as the primary glass former. Fluorophos-
phate glasses, designated FK-5 and FK-50 by
Schott, have very low optical dispersion, with
Abbe numbers of 70.4 and 81.5, respectively. 2.2.4. Borosilicate and Aluminosilicate
Glasses
Germanate and Germanosilicate Glasses. Borosilicate Glasses. Network modifiers
The viscosity of molten GeO2 (mp 1389 K) is cause a change from trigonal to tetrahedral coor-
633 Pa · s at 1673 K. For comparison vitreous dination in borosilicate glasses just as in borate
silica with < 10 ppm water has a viscosity of glasses. Addition of boron to silica melts reduces
8.17×108 Pa · s at the same temperature. Addi- the melt viscosity, as shown in Table 7; how-
tion of alkali lowers the viscosity of molten ger- ever, the effect is substantially less pronounced
mania substantially, as shown in Table 6. The than that produced by addition of alkali to silica
GeO2 – SiO2 glass system finds application in melts.
optical waveguides. The variation of viscosity
of GeO2 – SiO2 glass (42.2 mol % GeO2 ) with Table 7. Melt viscosity in the B2 O3 – SiO2 system (1573 K)
temperature is shown below: B2 O3 , mol % Viscosity, Pa · s
14.5
10 Pa · s (899 K) 0 (100 % SiO2 ) 1.622×1011
1013 Pa · s (992 K) 42.4 752
1012 Pa · s (1054 K)
62.4 78.6
71.9 25.4
82.5 10.2
The initial increase in density of molten 90.0 5.8
GeO2 with the addition of alkali is attributed to 93.9 4.4
changes in oxygen coordination around germa- 100.0 3.0

nium from tetrahedral to octahedral. This coor-

Many technically important glasses have
dination change is associated with the so-called
been developed on the basis of the boron
germanate anomaly, which gives rise to ob-
anomaly, i.e., a minimum or maximum in cer-
served maxima and minima in property – com-
tain physical properties of alkali borates at 15 –
position curves (e.g., molar volume, viscosity,
30 mol % modifier. Replacement of alkali by
acoustic velocity, and heat of solution).
boric acid decreases the thermal expansion of the

glass. The chemical resistance of these glasses
is excellent. Phase separation of borosilicate
glasses into silica- and borate-rich parts com-
monly occurs during heat treatment and is use-
ful in certain applications. For example, Vy-
cor glasses are based on liquid immiscibility in
the Na2 O−B2 O3 −SiO2 system. Most commer-
cial borosilicate glasses, however, have com-
positions that are miscible and homogeneous.
Borosilicate glasses are used in ovenware, lab-
oratory equipment, piping, and sealed-beam
headlights and in glass fibers for reinforcement,
textile, or insulation fiber applications.
Aluminosilicate Glasses. The addition of
small amounts of alumina (up to 4 mol %) to sil-
ica melts tends to increase the density of the re-
sulting glass, presumably because of the forma-
tion of triclusters (i.e., oxygen atoms connected
to one aluminum and two silicon atoms). The ef-
fect of large amounts of alumina on the viscosity
of aluminosilicate melts at 2223 K is comparable
to that of Li2 O at 1673 K (see Table 8).
Structural rules, based on X-ray diffraction
analysis of crystalline network-modifier alumi-
nosilicates, suggest that aluminosilicate glass
has a silica-like structure in which all oxygen
atoms are bridging when the molar ratio of al-
kali metal or alkaline earth to alumina is one. The
high viscosity of alkali aluminosilicate melts is
supposed to reflect this silica-like structure. For
example, a melt of composition Na2 O · Al2 O3 ·
6 SiO2 (albite) has a viscosity of 230 Pa · s at
1973 K, 582 K above the melting point of the
crystalline phase. On the other hand, a melt
of composition CaO · Al2 O3 · 2 SiO2 (anorthite)
is fluid (0.96 Pa · s at 1973 K, 143 K above the
melting point of the crystalline phase), indicat-
ing that silica-like behavior does not necessarily
occur in alkaline-earth aluminosilicate melts. In
contrast, however, the viscosity of fused silica at
1973 K is 2.48×106 Pa · s, so that neither of the
two aluminosilicate melts seems to be particu-
larly silica-like in its rheological properties.
Aluminosilicate glasses are used commer-
cially because they can withstand elevated tem-
perature and be chemically strengthened by
alkali-metal or alkaline-earth exchange. Appli-
cations, therefore, include airplane and space ve-
hicle windows, frangible containers, lamp en-
velopes, and cooking utensils.
Glass 17
Table 8. Viscosity of molten aluminosilicates (2223 K)
Al2 O3 , mol % Viscosity, Pa · s
0 1.72×104
6.2 1.80×102
12.9 70.0
20.2 3.90
50.0 0.20
70.0 0.10
100 0.042 ∗
∗ 2327 K.
2.2.5. Lead Silicate Glasses
The PbO−SiO2 system has the largest glass-
forming region among oxide glasses. Charac-
teristically, PbO also exhibits extended glass-
forming regions with other network formers.
The behavior of lead as a network modifier or
former is thought to arise from its low coordi-
nation number with oxygen, which varies bet-
ween 2 and 4. Note that although crystalline
Pb2 SiO4 has the orthosilicate composition com-
monly indicative of Q0 silica species, its actual
local silicon environment is Q2 , the silica tetra-
hedra in this compound forming Si4 O12 rings. In
this compound, bridging (Si−O−Si), nonbridg-
ing (Si−O−Pb), and nonbonding (Pb−O−Pb)
oxygen atoms are present. The last type is tetra-
hedrally coordinated to lead atoms, forming a
quadricluster [91], [92].
Lead glasses can be melted easily; they have
a long working range, low surface tension, and
high refractive index. These properties make
them useful for lead crystal, optical glass, and
hand-formed art ware. Lead-containing glasses
effectively absorb high-energy radiation and are,
therefore, used for radiation windows, fluores-
cent lamp envelopes, and television tubes. Low-
melting solder glasses and frit or decorative
enamels are usually based on low-melting lead
silicate compositions.
2.2.6. Chalcogenide Glasses
Glasses based on sulfur, selenium, or tellurium
rather than oxygen are well known. Chalco-
genide glasses are defined as noncrystalline
solids from melts of the three chalcogens and
18 Glass
their combination with elements of groups 14,
15, and 17. Structurally such glasses are quite
different; they resemble organic polymers rather
than oxide glasses. These glasses, although often
opaque to visible light, transmit further into the
infrared than oxide glasses. Many of the chalco-
genide glasses are semiconductors; the conduc-
tivity increasing with increasing atomic number.
Chalcogenide glasses tend to be much more sta-
ble than fluoride glasses.
2.2.7. Halide Glasses
Spectacular developments have occurred in flu-
oride glass. Before about 1974, the only well-
known fluoride glass was BeF2 , with tetrahe-
drally coordinated beryllium, a viscosity on the
order of 105 Pa · s at its melting point (813 K),
and a connectivity analogous to that observed for
silica. Heavy-metal fluoride glasses containing
zirconium, barium, and lanthanum (ZBL), with
a characteristic viscosity at the melting point
(813 K) of ca. 0.1 Pa · s, and the more stable
ZBLA glasses (57 mol % ZrF4 , 34 mol % BaF2 ,
5 mol % LaF3 , and 4 mol % AlF3 ) have been
discovered and examined [93]. Their use in op-
tical fibers is discussed in [94]. They are com-
mercially available.
Vitreous beryllium fluoride is a prime can-
didate in the production of optical waveguides
because of its unique spectral properties, includ-
ing transmission from < 160 to 5500 nm; very
low refractive index, nD = 1.275; and very low
dispersion, ν −1 = 9.3 × 10−3 .
Drawbacks are that it is highly hygroscopic
and contains beryllium, which is toxic. The for-
mer can be reduced by the addition of aluminum,
alkali-metal or alkaline-earth fluorides.
Some difficulties must be overcome in the
application of heavy-metal fluorides in waveg-
uides: two of the more serious are poor mechani-
cal strength and scattering loss due to transition-
metal ion impurities and crystalline inclusions.
2.2.8. Glasses with Complex Composition
Most industrially important glasses contain a
large number of components. The composition
of these glasses is given in Table 9. The sim-
ple systems already mentioned give some guide
about what to expect of the properties and struc-
ture in such systems. However, attempts are still
being made to relate properties to melt or glass
structure even for simple systems. The struc-
ture – property relationship in complex systems
is still largely obscure, and substantial scope re-
mains in glass production for classical heat and
beat treatments.
Figure 11. Observed and calculated nucleation and growth
regions as a function of temperature for Li2 O · 2 SiO2 glass
3. Glass Formation, Crystallization,
and Liquid Immiscibility
Glasses are thermodynamically unstable, com-
pared with isochemical crystals. The reason for
glass formation can be inferred from the work
of Tammann [95], among others, who showed
that the crystallization process occurs in two
steps: first crystal nuclei form, then these nu-
clei grow. Depending on the temperature and
the substance, either step may determine the
rate of spontaneous crystallization. Therefore,
at least two free energy barriers are involved in
the metastability of the supercooled liquid. The
first of these is the free energy of crystal nucleus
formation, arising primarily because the melt-
ing point of small crystals is lower than that of
large crystals. The second barrier is due to im-
peded molecular motion at the crystal – liquid
interface in going from a liquid to a crystal-like
position. The two noncoinciding regions of nu-
cleation and growth are shown for the Li2 O –
2 SiO2 system in Figure 11. This figure also
Table 9. Composition of some industrially important glasses (wt %)

Use Glass SiO2 Al2 O3 B2 O3 Li2 O Na2 O K2 O MgO CaO BaO PbO ZnO Others
code

Lamp bulbs, sealing 0080 73 1 17 4 5

Lamp tubing 0120 56 2 4 9 29
Color TV neck 0137 52.5 1 0.5 13 28 SrO : 5
Color TV funnel 0138 54 2 6 8 2 3 23
Lead glass for Steuben 0160 56 1 1 8 4 31 Sb2 O3 : 1, As2 O3 : 0.2
Microsheet 0211 65 2 9 7 7 7 TiO2 : 3
Consumer wave 0281 74 1 1 14 9 Sb2 O3 : 0.3, As2 O3 : 0.1
Aircraft windows 0317 61 17 13 3 3 0.4 TiO2 : 1, As2 O3 : 1
Tape reel 0320 63 12 13 5 6 Cl : 0.4
Aircraft windows 0331 66 21 4 9 0.2 1
Ferrite seal 1415 33 2 10 1 48 2 ZrO2 : 5, Sb2 O5 : 0.2,
As2 O3 : 0.1
Electron tubes 1723 57 16 4 7 10 6
T/H lamp 1724 57 17 5 6 8 8
Heat ABS 4605 23 14 1 4 FeO : 2, P2 O5 : 57
Table ware 6720 60 10 1 8 2 5 10 F− : 4
Series sealing 7050 68 2 24 6
Kovar sealing 7052 64 8 19 1 2 3 3 F−
Kovar sealing 7056 68 3 18 1 1 9
Substrate 7059 49 10 15 25 As2 O3 : 1
Low-loss electrical 7070 72 1 25 0.5 0.5 1
Auto sealed beam lamps
and bakeware, Pyrex 7251 82 2 12 4
Solder sealing 7570 3 11 12 74
Tungsten sealing 7720 74 1 15 4 6
Dental restorations 7724 51 8 9 32
Laboratory ware,
Kimax, Pyrex 7740 81 2 13 4
General 7760 78 2 15 3 1 As2 O3 : 1
Pharmaceutical 7800 72 6 11 7 1 1 2
Vycor high temperature 7913 96.5 0.5 3
Optical 7940 99.9
U.C.E. optical 7971 93 H2 O : 0.1
Glass
19
Table 9. (Continued)

20
Use Glass SiO2 Al2 O3 B2 O 3 Li2 O Na2 O K2 O MgO CaO BaO PbO ZnO Others
code

Ophthalmics 8078 44 6 1 21 24 4 La2 O3 : 2, TiO2 : 3.0, ZrO2 : 5,

As2 O3 : 0.1, Sb2 O3 : 0.1
Ophthalmics 8092 62 3 8 9 3 12 TiO2 : 0.7, Sb2 O3 : 0.4,

Glass
SO3 : 0.2, As2 O3 : 0.2,
B2 O3 : 1.0
Electron tubes, sealing 8160 56 2 3 10 1 5 23 F− : 0.7
Electron tubes, sealing 8161 39 6 2 51 Rb2 O : 2
Ophthalmics 8361 68 2 8 9 4 4 TiO2 : 0.4, Sb2 O3 : 0.5,
As2 O3 : 0.10
CRT panel 9025 68 4 12 3 5 6 TiO2 : 1, CeO2 : 1
Color TV panel 9068 65 2 7 9 1 2 2 2 SrO : 10, F− , TiO2 , CeO2 ,
As2 O3 , Sb2 O3
UV-transmitting 9741 65 5 27 1 2 F−
Optical N16B 5 34 2 6 ZrO2 : 6, La2 O3 : 41, CdO : 6
Laboratory ware G20 76 5 7 6 1 1 4
Reinforcement fiber E-Glass 54 14 <10 <0.5 <0.5 4.5 20 TiO2
Insulation fiber T-Glass 59 4.5 3.5 11 0.5 5.5 16
Chemical-resistant fiber C-Glass 65 4 5.5 8 0.5 3 14
Insulation fiber SF-Glass 59.5 5 7 14.5 ZrO2 : 4, TiO2 : 8, F−
High strength S-Glass 65 25 10
Container-Glass ∗ 71.9 1.7 12 – 13.9 0.4 3.6 7.9 0.3 SO2 : 0.2, F2 : 0.2, Fe2 O3 : 0.04
Window sheet ∗ 71 – 73 0.5 – 1.5 12 – 15 1.5 – 3.5 8 – 10
Plate glass ∗ 71 – 73 0.5 – 1.5 12 – 14 1–4 10 – 12

∗ Composition changes depending on regional variations in the USA: these compositions are characteristic for the North East.

illustrates the discrepancy between the nucle-
ation area derived from classical nucleation the-
ory and that observed experimentally [96], [97].
The rate of crystallization of an undercooled
liquid is specified by the rate of both crystal nu-
cleation and crystal growth at the expense of the
liquid. With glass, crystallization is called devit-
rification, which occurs when the glass is heated
above the glass transition temperature T g but
below the liquidus temperature. Glass transition
temperatures are given in Table 10.
Table 10. Glass transition temperatures and melting points for
some silicate glasses [80]
Glass Tg, K
SiO2 1381
Na2 Si3 O7 790
Na2 Si2 O5 725
K2 Si4 O9 775
K2 Si3 O7 820
K2 Si2 O5 763
CaMgSi2 O6 1026
NaAlSi3 O8 1088
1028
1036
KAlSi3 O8 1178
CaAl2 Si2 O8 1086
1153
In undercooled liquids, nucleation at inter-
faces (i.e., heterogeneous nucleation) dominates
other nucleation processes. Homogeneous nu-
cleation (i.e., nucleation in the interior of the
liquid in the apparent absence of an inter-
face) is known for only a few glass systems
(e.g., Li2 O · 2 SiO2 , Na2 O · 2 CaO · 3 SiO2 , and
BaO · 2 SiO2 [98]). Locations in which hetero-
geneous nucleation occurs are at the air – liq-
uid interface, the liquid container wall, parti-
cles or gas bubbles, and boundaries between
immiscible regions. A well-known example of
the predominance of heterogeneous nucleation
is the formation of ice, which nucleates hetero-
geneously at 273 K and homogeneously in un-
dercooled water at ca. 233 K.
Crystallization in undercooled liquids is con-
trolled primarily by the rate of crystal growth.
Nucleation studies by Tamman [95] of silicate
melts indicated that the rate of crystal growth
increases with increasing undercooling, reaches
a maximum, and then decreases with further in-
crease in undercooling. Theoretical studies in
the early 1930s showed that the growth rate in-
Glass 21
creases with increasing undercooling, but de-
creases with increasing viscosity, which ac-
counts for the experimentally observed maxi-
mum rate of crystal growth at some intermediate
temperature.
A measure of glass-forming tendency is indi-
cated by the reciprocal of the growth rate. Thus,
peak growth rates of 2×10−6 , 1×10−5 , and
1.5×10−2 cm/s for cristobalite (SiO2 ), GeO2 ,
and anorthite (CaAl2 Si2 O8 ), respectively, indi-
cate the first glass to be substantially more sta-
ble than the last. Some additional examples are
given in Table 11.
As a rule, technical glasses have peak growth
T m, K
rates below 10−3 cm/s. Some optical glasses
have peak growth rates greater than 10−2 cm/s,
1996 thereby causing considerable production prob-
1073
1147 lems.
1043 Growth rates are generally extremely depen-
1198 dent on composition. Alkali – silica systems are
1318
1665
illustrated in Figure 12. Even minor compo-
1391 nents can substantially influence growth rate
1391 and, hence, the ability to form a glass. The role
1391 of minor components is usually thought to be
1806
1826
one of poisoning the surface of the crystallite.
1826 Nucleation and growth are diffusion-
controlled. Glasses, therefore, become more
stable with increasing number of components.
Consideration of the Stokes – Einstein relation,
which describes the inverse proportionality bet-
ween diffusion and viscosity, suggests that lower
diffusion and, therefore, higher viscosity at the
melting temperature enhance the glass-forming
tendency. Increasing the concentration of net-
work formers, therefore, tends to enhance melt
viscosity and decrease crystal growth for the
same thermodynamic driving force of crystal-
lization.
In addition to crystalline precipitation, phase
separation can occur in specific glass systems.
Such separation is usually manifested as changes
in color, optical transparency, or chemical dura-
bility. Glass systems exhibiting phase separa-
tion possess, in a specific temperature region,
a miscibility gap characterized at the upper and
lower ends by an immiscibility temperature. Liq-
uid immiscibility can be made visible by proper
heat treatment, especially in glasses that tend
to undergo phase separation, e.g., those found in
the silica-rich part of the Li2 O – 2 SiO2 and alka-
line earth – silica systems. The growth rate of the
secondary glassy phase, separated from the orig-
22 Glass
Table 11. Measured growth rate of minerals and related substances [80]

Crystal Composition Liquidus ∆T at peak, K Rate at peak, cm/s

temperature, K
Cristobalite SiO2 1996 50 2×10−6
Anorthite CaAl2 Si2 O8 1830 300 1.5×10−2
Diopside CaMg (SiO3 )2 1664 >100 2.2×10−2
Na2 Si2 O5 1147 60 1×10−3
GeO2 1389 100 1×10−5
SrB4 O7 1270 100 1.6×10−2
PbB4 O7 1048 120 2×10−4
Alkali Ab70 Or30 · 1243 160 3.2×10−6
feldspar 1.7 % H2 O

inal homogeneous glass, is diffusion-controlled 4. Chemical, Mechanical, and

in most cases.
Figure 12. Critical cooling rate as a function of composition
for alkali – silica melts (R2 O – SiO2 ) [99]
For example, opal glasses may be either
translucent or opaque, depending on the par-
ticle size and quantity of the second phase
and on the difference in refractive index bet-
ween the second phase and the matrix. Fluorine-
containing glasses, which separate into phases
containing NaF or CaF2 , are commonly made
into pressed items such as tableware. On cool-
ing, such glasses become spontaneously opaque,
phase-separating into a silicate-rich matrix and
fluoride droplets with dimensions of the order
of 10−6 m. Other products in which phase sep-
aration is used are Vycor glass, photochromic
glass, and luminescent and magnetic glasses.
Physical Properties of Industrially
Important Melts and Glasses
Extensive research has been carried out on the re-
lation between composition and physical prop-
erties of multicomponent glass systems. Partial
molar coefficients for most physical properties
(e.g., expansion, viscosity, heat capacity, and re-
fractive index) have been determined since the
pioneering work in this area by Winckelmann
and Schott [100], enabling calculation of prop-
erties for a given composition. Some properties
of industrially important glasses are collected in
Table 12, 13, 14, 15.
The lack of proper probes to analyze glass
structure has prevented derivation of quantita-
tive relationships between glass structure and
properties. Qualitative rationalizations in terms
of one model or another abound, and with such
models, predictions can be made as to the influ-
ence of various components on the physical and
structural nature of the glass.
The most important property of a glass or
melt is its viscosity. Therefore this discussion
starts with the rheological properties of glass
melts and the three major variables which in-
fluence these properties: temperature, time, and
glass composition. Next, surface tension of
melts is discussed, followed by glass density,
thermal expansion, mechanical properties such
as elasticity and mechanical strength, hardness,
thermal properties, electrical properties, gas per-
meability, chemical stability, surface properties
and optical properties. This chapter concludes
with a discussion of the nature of color in glasses.
 Glass 23
Table 12. Properties of some industrially important glasses

Type of glass Glass Color Forms usually Corrosion resistance

a
code available b Class Weathering Water Acid

Soda lime 0080 clear BMT I 3 2 2

Potash soda lead 0120 clear TM I 2 2 2
Alkaline earth lead 0137 clear T
Potash soda lead 0138 clear P II 1 3
Lead crystal for Steuben 0160 clear
Potash soda zinc 0211 clear S I 1 2
Sculptured ware 0281 3 2
Aircraft windows 0317 clear S 1 3
Tape reel 0320
Pipets and centrifuge tubes 0331 T
Ferrite sealing glass 1415 Powder disks
cane
Aluminosilicate 1723 clear BT I 1 1 3
Halogen cycle lamps 1724 clear T 2
Heat-absorbing, 4605 gob strip
visible-transmitting pressing
d
Soda zinc 6720 opal P I 1 2
Borosilicate 7050 clear T II 3c 3c 4c
Borosilicate 7052 clear BMPT II 2c 2c 4c
Borosilicate 7056 clear BTP II 2 2 2
Barium−bariumsilicate 7059 clear S II 1 4
Borosilicate 7070 clear BMPT I 2c 2c 2c
Borosilicate 7251 clear P I 1c 2c 2c
High lead 7570 clear II 3 3 4
Borosilicate 7720 clear BPT I 1 2c 2c
Frit for dental restorations 7724 white ground and 2 4
screened
cullet
Borosilicate 7740 clear BPSTU I 1c 1c 1c
Borosilicate 7760 clear BP I 2 2 2
Soda barium borosilicate 7800 clear T 1 1 1
96 % Silica 7913 clear BPRST I 1 1 1
Fused silica 7940 clear U I 1 1 1
Titanium silicate 7971 clear U 1 1 1
Ophthalmic lens blanks 8078
Ophthalmic lens blanks 8092
Potash soda lead 8160 clear PT II 2 2 3
Potash lead 8161 clear PT I 2 1 4
Ophthalmic lens blanks 8361 2 2
Alkali−barium 9025 clear P II 3 2
Alkali−strontium 9068 clear P I 2 2
Borosilicate 9741 clear BUT II 3c 3c 4c
Borosilicate N16B clear
Aluminoborosilicate G20 clear BPT
Lime−aluminoborosilicate E-glass clear F
Soda lime−aluminoborosilicate T-glass clear F
Soda lime−borosilicate C-glass clear F
Soda−titania−zirconia SF-glass clear F
Magnesium−aluminosilicate S-glass clear F
a
Glasses 7905, 7910, 7911, 7912, 7913, and 7917 for special UV and IR applications. Glass 1720 is available with improved UV
transmittance (designated glass 9730). Glass 7760 is also available with special transmission suitable for sun lamps. b B = blown
ware; M = multiform; U = panels; P = pressed ware; R = rolled sheet; C = castings; S = plate glass; T = tubing and rod; F = fiber.
c
These borosilicate glasses may rate differently if subjected to excessive heat treatment. d Since weathering is determined primarily
by clouding which changes transmission, a rating for the opal glasses is omitted.
24 Glass
Table 13. Properties of some industrially important glasses (continued)

Type of glass Thermal Upper application temperatures g Thermal shock

expansion, resistance h ,
×10−7 ◦ C e (mechanical consideration only) plates 15×15 cm,
annealed
0– 25 ◦ C Annealed Tempered 3.2 mm 6.4 mm12.7 mm
to
300 ◦ C setting NormalExtreme Normal Extreme thick, thick, thick,
◦ ◦ ◦
point service,service, service, service, C C C
◦ ◦ ◦ ◦
C C C C

Soda lime 93.5 105 110 460 220 250 65 50 35

Potash soda lead 89.5 97 110 380 65 50 35
Alkaline earth lead 97.0 102
Potash soda lead 98.5 109
Lead crystal for Steuben 93
Potash soda zinc 74.0 84.0
Sculptured ware 87
Aircraft windows 87 98
Tape reel 70.7
Pipets and centrifuge tubes 75.5
Ferrite sealing glass 79 96.7
Aluminosilicate 46 54 200 650 400 450 125 100 70
Halogen cycle lamps 43 50
Heat-absorbing, visible-transmitting 54
Soda zinc 78.5 90 110 480 220 275 70 60 40
Borosilicate 46 51 200 440 235 235 125 100 70
Borosilicate 46 53 200 420 210 210 125 100 70
Borosilicate 51.5 56 200 460
Barium−bariumsilicate 46 50.5
Borosilicate 32 39 230 430 230 230 180 150 100
Borosilicate 36.5 41.4 230 460 260 260 160 130 90
High lead 84 92 100 300
Borosilicate 36 43 230 460 260 260 160 130 90
Frit for dental restorations 52.6
Borosilicate 32.5 35 230 490 260 290 160 130 90
Borosilicate 34 37 230 450 250 250 160 130 90
Soda barium borosilicate 50 53 200 460
96 % Silica 7.5 900 1200
5.5 f
Fused silica 5.6 900 1100
3.5 f
Titanium silicate 0.5 −2 800 1100
Ophthalmic lens blanks 91.4
Ophthalmic lens blanks 94
Potash soda lead 91 100 100 380 65 50 35
Potash lead 90 99 100 390
Ophthalmic lens blanks 94
Alkali−barium 90.0 98.0
Alkali−strontium 99.0 111
Borosilicate 39.5 50 200 390 150 120 80
Borosilicate 87
Aluminoborosilicate
Lime−aluminoborosilicate 60
Soda lime−aluminoborosilicate 80
Soda lime−borosilicate 72
Soda−titania−zirconia 75
Magnesium−aluminosilicate 34
e
Code 9608 may be produced in a range of expansion values depending upon intended application. f Extrapolated values.
g
Normal service: no breakage from excessive thermal shock is assumed. Extreme limits; glass will be very vulnerable to
thermal shock. Recommendations in this range are based on mechanical stability considerations only. Tests should be made
before adopting final designs. These data approximate only. h These data approximate only. Based on plunging cold sample into
cold water after oven heating. Resistance of 100 ◦ C means no breakage if heated to 110 ◦ C and plunged into water at 10 ◦ C.
Tempered samples have over twice the resistance of annealed glass.
 Glass 25
Table 14. Properties of some industrially important glasses (continued)

Type of glass Thermal Viscosity data j Knoop Density, Young’s Poisson’s

stress hardness, modulus,
resistance, Strain Annealing Softening Working HK200 k g/cm3 GPa ratio
◦ i
C point, ◦ C point, ◦ C point, ◦ C point, ◦ C
Soda lime 16 473 514 696 1005 465 2.47 70 0.22
Potash soda lead 20 395 435 630 985 382 3.05 59 0.22
Alkaline earth lead 436 478 661 977 3.18
Potash soda lead 450 490 670 3.02
Lead crystal for Steuben 367 405 583 3.09
Potash soda zinc 20 508 550 720 1008 2.57 74 0.21
Sculptured ware 500 540 719 2.48 0.22
Aircraft windows 574 624 871 440 2.45 73 0.22
Tape reel 463 493 638 2.38
Pipets and centrifuge tubes 510 548 2.41
Ferrite sealing glass 620 654 776 3.74
Aluminosilicate 26 665 710 908 1168 514 2.64 86 0.24
Halogen cycle lamps 613 722 926 1200 572 2.64 85 0.24
Heat-absorbing, 560 612 806 2.52
visible-transmitting
Soda zinc 20 505 540 780 1023 2.58 70 0.21
Borosilicate 39 461 501 703 1027 2.24 60 0.22
Borosilicate 41 436 480 712 1128 375 2.27 57 0.22
Borosilicate 33 472 512 718 1058 2.29 64 0.21
Barium−bariumsilicate 32 593 639 844 1160 2.76 68 0.28
Borosilicate 66 456 496 1068 2.13 51 0.22
Borosilicate 48 521 565 808 1192 451 2.26 64 0.19
High lead 21 342 363 440 558 5.42 55 0.28
Borosilicate 49 484 523 755 1146 2.35 63 0.20
Frit for dental restoration 633 671 847 2.96
Borosilicate 54 510 560 821 1252 418 2.23 63 0.20
Borosilicate 52 478 523 780 1198 442 2.24 62 0.20
Soda barium borosilicate 33 533 576 795 1189 2.36
96 % Silica 220 890 1020 1530 487 2.18 68 0.19
Fused silica 286 956 1084 1580 489 2.20 73 0.16
Titanium silicate 3370 1000 1500 2.21 68 0.17
Ophthalmic lens blanks 506 544 686 4.02
Ophthalmic lens blanks 500 540 730 2.62
Potash soda lead 18 397 438 632 973 2.98
Potash lead 22 400 435 600 862 3.99 54 0.24
Ophthalmic lens blanks 500 543 726 1032 2.54 0.23
Alkali−barium 421 460 647 988 2.60
Alkali−strontium 462 503 688 2.68
Borosilicate 54 408 450 705 1161 2.16 49 0.23
Borosilicate 19 540 720 1065 2.48
Aluminoborosilicate 524 569 794 1190 2.39 72
Lime-aluminoborosilicate 507 657 846 2.60 74
Soda 715 2.54
lime−aluminoborosilicate
Soda lime−borosilicate 435 585 752 2.61 70
Soda−titania zirconia 675 2.57
Magnesium−alumino 760 810 970 87
silicate
i
Resistance in ◦ C is the temperature differential between the two surfaces of a tube or a constrained plate that will cause a tensile
stress of 6.9 MPa (1000 psi) on the cooler surface. j These data subject to normal manufacturing variations. k Determined by
revised ASTM standard: number of standard not yet assigned.
26 Glass
Table 15. Properties of some industrially important glasses (continued)

Type of glass Log10 of volume resistivity, Ω · cm Dielectric properties at 1 MHz, 20 ◦ C

25 ◦ C 250 ◦ C 350 ◦ C Power Dielectric Loss factor, Refractive

factor, % constant % index m
Soda lime 12.4 6.4 5.1 0.9 7.2 6.5 1.512
Potash soda lead >17 10.1 8.0 0.12 6.7 0.8 1.560
Alkaline earth lead 10.1 8.4 1.570
Potash soda lead 7.7 1.563
Lead crystal for Steuben 1.569
Potash soda zinc 1.52
Sculptured ware 6.5 5.2 1.515
Aircraft windows 5.5 4.3 8.94 1.506
Tape reel
Pipets and centrifuge tubes
Ferrite sealing glass
Aluminosilicate >17 13.5 11.3 0.16 6.3 1.0 1.547
Halogen cycle lamps 13.8 11.8 1.54
Heat-absorbing, 1.51
visible-transmitting
Soda zinc 1.507
Borosilicate 16 8.4 6.8 0.33 4.9 1.6 1.479
Borosilicate 17 9.2 7.4 0.15 5.1 1.3 1.484
Borosilicate 10.2 8.3 0.27 5.7 1.5 1.487
Barium−bariumsilicate 13.1 11.0 5.9 1.53
Borosilicate >17 11.2 9.1 0.06 4.1 0.25 1.469
Borosilicate 18 8.0 6.5 0.45 4.9 2.18 1.476
High lead >17 10.6 8.7 0.22 15 3.3 1.86
Borosilicate 16 8.9 7.3 0.23 4.6 1.3 1.487
Frit for dental restoration 1.523
Borosilicate 15 8.1 6.6 0.39 4.6 2.6 1.474
Borosilicate 17 9.4 7.7 0.16 4.6 0.79 1.473
Soda barium borosilicate 7.0 5.7 1.491
96 % Silica >17 9.7 8.1 0.04 3.8 0.15 1.458
Fused silica >17 12.4 10.7 0.001 3.8 0.0038 1.459
Titanium silicate 20.3 12.2 10.1 <0.002 l 4.0 l <0.008 l 1.484
Ophthalmic lens blanks 1.70
Ophthalmic lens blanks 1.523
Potash soda lead >17 10.6 8.4 0.09 7.0 0.63 1.553
Potash lead >17 12.0 9.9 0.06 8.3 0.50 1.659
Ophthalmic lens blanks 8.7 6.9 1.523
Alkali−barium 8.5 6.8 6.5 1.523
Alkali−strontium 9.3 7.4 1.529
Borosilicate >17 9.4 7.6 0.32 4.7 1.5 1.468
Borosilicate 5.8 4.7 7.7 1.4
Aluminoborosilicate 7.4 6.0 0.51 4.9 2
Lime-aluminoborosilicate 6.4 1.548
Soda 7.3 1.541
lime−aluminoborosilicate
Soda lime−borosilicate 7.8 1.549
Soda−titania zirconia 8.3 1.537
Magnesium−alumino silicate 1.523
l
At 10 kHz. m Refractive index may be either the sodium yellow line (589.3 nm) or the helium yellow line (587.6 nm). Values at
these wavelengths do not vary in the first three places beyond the decimal point.

4.1. Rheological Properties of Glass
Melts
Viscosity determines the optimum melting,
forming, and annealing procedures for a glass,
as well as the limitations on its use at high tem-
perature. The optimal viscosity regions for these
processes are illustrated in Figure 13. A charac-
teristic of glass is that rapid but smooth changes
in viscosity occur in the entire region from 10
to 1013 Pa · s, provided that no devitrification or
crystallization occurs. Molten silicates with vis-

cosity up to 103 Pa · s are Newtonian liquids,
i.e., liquids in which viscosity is independent
of shear stress.
Figure 13. Optimum viscosity regions for forming and an-
nealing glasses
Four types of viscosity measurement exist:
(1) stationary methods, which include capillary
and falling body; (2) rotation methods, including
cone-and-plate and rotating cylinders; (3) oscil-
lating methods; and (4) bending beam methods.
No single instrument can measure viscosity over
the entire range of interest for glasses. Below
106 Pa · s a cone-and-plate or rotation viscome-
ter is used. In the range 106 – 1011 Pa · s, a wire
pull method is used. The parallel-plate method
covers the 104 – 108 Pa · s range. The bending
beam method is used for viscosities of 108 –
1014 Pa · s. A synopsis of methods for viscosity
measurement is given in [101] and [102].
Glass 27
4.1.1. Temperature Dependence of Viscosity
The temperature dependence of viscosity is
shown for some oxide glasses in Figure 14. The
working, softening, annealing, and strain points
are indicated as reference temperatures. Defini-
tion of these points are given by the ASTM.
Figure 14. Temperature dependence of viscosity for some
industrial glasses
a) Glass no. 8363; b) Glass no. 0010; c) Glass no. 7070;
d) Glass no. 0080; e) Glass no. 7740; f) Glass no. 1720;
g) Glass no. 7900; h) Glass no. 7940, fused silica; i) Nitrided
96 % SiO2
The working point of a glass melt is the
temperature at which its viscosity is exactly
103 Pa · s; the glass is then sufficiently fluid for
forming by most methods. The working range is
the range of surface temperature in which glass
is formed into ware in a specific process. The up-
per end is the temperature at which glass is ready
for working and corresponds generally to a vis-
cosity of 102 – 103 Pa · s. The lower end refers
to the temperature at which glass is sufficiently
viscous to hold its formed shape, corresponding
to a viscosity ≥103 Pa · s.
The softening point is defined, according to
ASTM C 338 as the temperature at which a uni-
form fiber of glass with a diameter of 0.55 –
0.75 mm and a length of 23.5 cm increases its
length by 1 mm/min when the upper 10 cm is
heated at a rate of 5 ◦ C/min. The viscosity at the
softening point depends on the density and sur-
face tension of the glass, and is 106.6 Pa · s for a
glass with a density of 2.5 g/cm3 and a surface
tension of 0.3 N/m.
28 Glass
The annealing point is the temperature cor-
responding to a viscosity of approximately
1012 Pa · s. At this point, internal stress is
released to an acceptable value of 1.7 MPa
(250 psi) in about 15 min.
Finally, the strain point corresponds to the
temperature at which internal stresses are re-
duced to an acceptable level of 1.7 MPa in about
4 h. The viscosity at this temperature is approx-
imately 1013.5 Pa · s. This point represents the
temperature of transition from viscoelastic to
brittle behavior. The glass transition tempera-
ture T g lies in this viscosity range. The tempera-
ture region between the annealing and the strain
points must be crossed with welldefined slow
cooling rates if strain-free large glass bodies are
to be produced. Both annealing and strain points
may be determined by fiber elongation, ASTM
C 336-71 (1981), or by beam bending, ASTM C
598-72 (1978).
In the parlance of glass science, glass with a
high softening point is known as hard glass; that
with a low softening point, as soft. If the temper-
ature interval corresponding to 102 – 106 Pa · s is
large, the glass is called sweet or long in con-
trast to short glasses with steep viscosity – tem-
perature curves. Long glasses, therefore, solidify
more slowly than short glasses on cooling. Com-
binations of these terms are also used; e.g., fused
silica, Corning Code 7940, would be identified
as a hard, long glass.
Viscosity decreases with increasing temper-
ature; for liquid metals and simple ionic melts,
the temperature dependence of the viscosity can
be represented by the exponential equation
η=η0 exp (Eη /RT )
where η is the viscosity and Eη the activation en-
ergy for viscous flow. This Arrhenius-type rela-
tion rarely holds for polymeric melts because of
depolymerization with increasing temperature.
Such depolymerization results in a decrease in
the activation energy for viscous flow.
For silicate melts, the temperature depen-
dence of viscosity is adequately represented by
the empirical Vogel – Fulcher – Tammann equa-
tion
B
logη=A+
(T − T0 )
in which A and B are constants, B being a mea-
sure of the activation energy for viscous flow;
T 0 is added as a third adjustable constant. A
Fulcher and two Arrhenius-type equations for
three network-forming pure liquid oxides are
given below:
For B2 O3 :
log (η, Pa·s) = 0.198 + 145.1/ (T − 443)
For GeO2 (1773 – 1973 K):
1.423 × 103
log (η, Pa·s) = − 0.4704
T
For SiO2 glass (1508 – 1608 K) and SiO2 melt
(1973 – 2273 K):
2.7115 × 103
log (η, Pa·s) = − 0.5884
T
The presence of suspended solid matter or
gas bubbles in the melt seriously affects mea-
surement of viscosity. The effect is usually
to increase the apparent viscosity. In addition,
non-Newtonian behavior is commonly observed
in crystal – melt slushes or melted gas bubble
foams.
4.1.2. Time Dependence of Viscosity
In some highly viscous melts a dependence of
viscosity on previous treatment of the melt and
on time has been observed, particularly in the
subliquidus area. The reason is that highly vis-
cous undercooled liquids do not relax rapidly
enough for the structural elements in the liquid
to rearrange themselves in a state commensurate
with the ambient temperature.
4.1.3. Composition Dependence of Viscosity
As shown previously, the addition of network
modifiers to liquid silicon dioxide, boron triox-
ide, or germanium dioxide strongly affects melt
viscosity. Also, among network modifiers, those
with the highest cationic field strength are most
effective in reducing viscosity.
Although the effect of network modifiers
such as alkali-metal and alkaline-earth atoms
is fairly well understood, the same cannot be
said for amphoteric oxides (e.g., Al2 O3 , ZnO, or
MgO). Their varying role is ascribed to changes

in coordination in melts with strong bases, giv-
ing rise to terms such as the germanium, alu-
minum, or boron anomaly.
Figure 15. Variation in connectivity of crystalline calcium
silicates and aluminates [103]
a) CaO−SiO2 system; b) CaO−Al2 O3 system
Consider the CaO−Al2 O3 −SiO2 system as
an illustration of the difficulty in deriving viscos-
ity for ternary systems. The known crystal struc-
tures in the two binary systems CaO−Al2 O3 and
CaO−SiO2 show that addition of calcium ox-
ide to silica decreases the connectivity of the
silica network in a regular fashion from Q4 to
Q0 ; however, addition of calcium oxide to alu-
mina results initially in a coordination change
for aluminum from six- to fourfold, followed
by the formation of network aluminates with
Q4 connectivity. These trends are illustrated in
Figure 15. The two tendencies, depolymeriza-
tion of silica and polymerization of alumina,
must be taken into account if the viscosity of
a CaO · 2 SiO2 · Al2 O3 melt is to be predicted.
Actual measurements indicate that the viscosity
Glass 29
of a CaO · 2 SiO2 melt at 1973 K is 0.78 Pa · s
and for CaO · Al2 O3 0.11 Pa · s, whereas a melt
with composition CaO · 2 SiO2 · Al2 O3 has a vis-
cosity of 0.96 Pa · s at the same temperature,
which suggests that the CaO · 2 SiO2 system is
viscosity-determining in this ternary system.
The viscosity of the CaO−Al2 O3 −SiO2 sys-
tem is still amenable to some rationalization.
The melting behavior in CaO−SiO2 – metal ox-
ide systems is more puzzling. As an example, the
variation in the three-phase liquidus boundary
between crystalline CaSiO3 – crystalline silica –
liquid, as a function of a third metal oxide, is
illustrated in Figure 16. The liquidus boundary
suggests that Cr2 O3 associates with CaO, which
extends the silica field with an attendant increase
in viscosity, in contrast to BaO, which decreases
the silica field most. One might expect concomi-
tant viscosity variations due to this extension or
contraction of the silica field in the CaO−SiO2
field. No compatible data are available to assess
whether this is indeed the case. Preliminary 29 Si
MAS NMR work has not shown variations in
the melt structure among (BaO, ZrO2 , Al2 O3 ,
B2 O3 , TiO2 )−CaO−SiO2 glass systems [106].
Figure 16. Variation in liquidus boundary in the CaO – SiO2
system as a function of a third added component [105]
The above examples serve to illustrate that
no acceptable mathematical formulation for the
relation between viscosity and glass composi-
tion exists; the viscosity of a glass is determined
by the superposition of several factors. The de-
pendence of viscosity on composition has been
30 Glass
examined in several systematic studies, but the
results are applicable only to special groups of
glasses. Examples include the effect of various
components on the viscosity of sodium silicate
glasses [107] and the determination of partial
molar viscosity coefficients for multicomponent
naturally occurring melt systems [108].
4.2. Surface Tension
4.3. Density
The density of most technical silicate glasses
is 2.2 – 2.5 g/cm3 . For molten B2 O3 , the den-
sity varies between 1.67 g/cm3 at 723 K and
1.49 g/cm3 at 1673 K; for a GeO2 melt at 1473 K,
the density is 3.46 g/cm3 ; for molten SiO2 , the
density variation between 2208 and 2438 K is
given by the equation
= 2.508 − 2.13 × 10−4 t
Surface tension is defined as the force needed
For molten Al2 O3 , the density variation over the
to increase the surface area of a material by
temperature range 2373 – 2623 K is given by
1 cm2 . The numerical value of this measure of
the strength of a surface is expressed in N/m.
Surface tension is an important variable for the
following reasons: it predicts the degree of wet-
ting between different melts, melt – metal, and
melt – tank lining surfaces; it predicts movement
toward the surface of ions that decrease surface
tension and away from the surface of ions that
increase surface tension; and it suggests a means
of removing gas bubbles in a melt.
The surface tension of silicate melts is not
= 5.370 − 11.46 × 10−4 t
Note that in both equations the temperature, t,
is in degrees Celsius. Components with high
molecular mass may increase the density to ca.
7 g/cm3 .
The molar volume derived from the density
is related to the average molecular mass of the
liquid
very sensitive to either composition (Fig. 17A)
or temperature (Fig. 17B), compared to melt
viscosity. Characteristic values for glasses and
other materials are given in Table 16. See also
Figure 17.
Table 16. Surface tension of various glasses and reference
materials
V = Σxi Mi /
where V is the molar volume, in cubic centime-
ters per mole;  is the density, in grams per cu-
bic centimeter; xi is the mole fraction; and Mi is
the gram molecular mass of pure component i.
In terms of partial molar volumes vi , the molar
volume is given by the sum

Surface tension, Temperature, V = Σxi vi

N/ m K
The volumetric deviation from ideal mixing is
Soda lime 0.33 1573
Silica 0.275 1673 defined by the difference
PbO2 – SiO2 melt 0.230 1675
B2 O3 melt 0.081 1173 ∆V =V −Videal =V −Σxi vi◦
H2 O 0.073 293
Molten alloy 0.60 where v◦i = molar volume of the pure component
i.
The density of oxide melts is commonly a
Most of the available data on interfacial ten- linear function of temperature over a relatively
sion are for systems of interest in ferrous metal- wide range. Densities are often calculated by us-
lurgy. Frequently, these measurements are made ing additive relations such as the following:
in relation to the study of specific problems 1 1
such as wetting characteristics of welding fluxes = Σ [pi /i ]
and dispersion of metal droplets in slags. The
Slag Atlas contains a discussion of such systems
[101].
 100
where  is the density, i the calculated partial
molar or mass density coefficient, and pi the con-
centration of component i in the liquid, in mol %
 Glass 31

Figure 17. Variation of melt surface tension

A) With composition: a) SiO2 (2341 K); b) SiO2 (1149 K); c) Al2 O3 – SiO2 (2300 K); d) CaO – SiO2 (1823 K); e) MnO – SiO2
(1773 K); f) MgO – SiO2 (1843 K); g) PbO – SiO2 (1573 K); h) Li2 O – B2 O3 (1173 K); i) Na2 O – B2 O3 (1173 K); j) K2 O –
B2 O3 (1173 K); k) Bi2 O3 – SiO2 (1313 K)
B) With temperature: a) 39.2 CaO · 15.4 Al2 O3 · 45.7 SiO2 ; b) 36.5 CaO · 63.5 SiO2 ; c) 40 FeO · 5 MgO · 55 SiO2 ;
d) 30.3 Li2 O · 69.7 SiO2 ; e) 30.1 Na2 O · 69.9 SiO2 ; f) 33.4 PbO · 66.6 SiO2 ; g) 31.2 K2 O · 68.8 SiO2 ; h) 32 Rb2 O · 68 SiO2 ;
i) B2 O3

or wt %. Coefficients for calculating the density duced stress frequently imposes operating lim-
of soda lime – magnesia glasses in weight per- its because the stress is directly proportional to
cent on the basis of pi are given below [109]: the rate of expansion. The feasibility of glass –
metal seals, processing, annealing, tempering,
SiO2 2.20
Na2 O 3.47
and strengthening depends on thermal expan-
CaO 5.00 sion. Thermal expansion is also a factor in de-
MgO 3.38 termining the ability of a glass article to survive
Al2 O3 2.75 thermal shock and thermal cycling.
Like most materials, glasses expand on heat-
Density is somewhat dependent on the de- ing and contract on cooling. Hysteresis is rarely
gree of cooling, slow rates of cooling giving a observed if thermal cycling is sufficiently slow.
higher density. Density measurements are fre- The linear expansion coefficient α is defined by:
quently used as quality control indicators in
glass plants because this property is very easy to α∆T = (L/L0 ) (∆L/∆T )
measure (sink – float technique) and deviations
from established standards indicate changes in where L 0 is the initial length, L is the length
glass composition. measured at temperature T , and ∆L the change
of length with a temperature change of ∆T . The
linear expansion coefficient is used extensively
in the glass industry. The variation of linear ther-
4.4. Thermal Expansion
mal expansion coefficient with temperature is
shown in Figure 18. The average coefficient of
The thermal expansion of glass is an important
linear expansion in the range 273 – 573 K is de-
property in many applications. Thermally in-
32 Glass
termined on annealed samples, as specified in
ASTM C 598-72 (1978).
Figure 18. Variation in linear expansion as a function of time
a) Undercooled fluid; b) Contraction curve on slow cooling;
c) Contraction curve on fast cooling; d) Slow reheating of
(c)T g and T g are the glass transition temperatures upon slow
and fast cooling, respectively.
Figure 19. Linear thermal expansion coefficients for some
industrial glasses
a) Glass no. 1990, Iron sealing; b) Glass no. 0120, Dumet
sealing; c) Glass no. 7052, Kovar sealing; d) Glass no. 7740;
e) Glass no. 7900, 96 % silica
Expansion curves are generally nearly linear
up to the glass transition temperature. Above
this, thermal expansion increases by a factor of
ca. 3 – 4 because of variations in vibrational am-
plitudes. The point at which the extrapolated
slopes of both segments of the curve intersect
is defined as the transformation temperature of
the glass, according to DIN 52 324.
Inspection of Figure 19 shows that the ther-
mal expansion of glasses can differ considerably.
Technical glasses are customarily classified ac-
cording to their coefficients of expansion:
Low expansivity: α < 60×10−7 K−1
High expansivity: α > 60×10−7 K−1
Characteristic values are
Pyrex 32×10−7 K−1
Soda lime glass 90×10−7 K−1
Cesium borate glass 30×10−7 K−1
Pure SiO2 glass has a linear expansion coef-
ficient α of 5.0×10−7 K−1 at 293 – 573 K. Ad-
dition of other oxides to silica may increase this
value to 125×10−7 K−1 . Most technical glasses
have a thermal expansion between that of Pyrex
(30×10−7 K−1 ) and commercial soda lime
glasses [(80 – 90)×10−7 K−1 ]. Glasses with ex-
pansion coefficients below 60×10−7 K−1 are
called hard glasses, whereas those with higher
expansion coefficients are designated as soft.
This distinction between hard and soft coincides
with high and low softening points as discussed
previously (Section 4.1.1).
Thermal expansion coefficients may be ra-
tionalized in terms of the degree of connectiv-
ity of the glass network. Introduction of net-
work modifiers increases the thermal expansion
of glasses. In the alkali – silica system, lithium
silicate glasses show the smallest thermal expan-
sion and potassium silicate glasses the largest.
This difference can be rationalized easily by in-
spection of thermal expansion and compress-
ibility as a function of coordination number of
selected metal –oxygen bonds (Table 17). The
observed α/β ratio is approximately constant
for many cation octahedra. Changes in bond
length during thermal expansion, therefore, tend
to be the inverse of those during compression.
Lithium, sodium, and potassium, with assumed
oxygen coordination variation between four and
eight in silicate melts, show a difference in R−O
expansion (∆α) of 42×10−7 K−1 . Partial molar
expansion coefficients have been calculated and
compiled [111].
The transformation temperature has been de-
fined as that point on an expansion – tempera-
ture graph at which straight lines drawn to the
thermal expansion curves above and below the
glass transition temperature intersect. Volume
changes in this transformation region are of great
practical use. A plot of expansion coefficient ver-
sus time is shown in Figure 18. The equilibrium
 Glass 33
Table 17. Predicted values of thermal expansion and compressibility for element – oxygen bonds in oxygen-based minerals [110]

Element Coordination number α×10−6 , K−1 −β×10−6 , kbar−1 α/β

Si(IV) 4 39
Ge(IV) 4 50
B(III) 4 39
Al(III) 4 65
Al(III) 6 8.2 83 0.099
Li(I) 4 16.4 274 0.060
Li(I) 6 19.5 353 0.055
Na(I) 6 19.5 499 0.063
Na(I) 8 20.6 606 0.034
K(I) 6 19.5 761 0.026
K(I) 8 20.6 875 0.024
K(I) 12 27.4 999 0.027
Rb(I) 6 19.5 884 0.022
Rb(I) 8 20.6 969 0.021
Cs(I) 8 20.6 1102 0.019
Mg(II) 6 13.8 167 0.071
Mg(II) 8 16.4 211 0.067
Ca(II) 6 13.8 243 0.057
Ca(II) 8 16.4 282 0.058
Sr(II) 6 13.8 303 0.046
Sr(II) 8 16.4 333 0.049
Ba(II) 6 13.8 368 0.038
Ba(II) 8 16.4 442 0.037
Co(II) 6 13.8 174 0.079
Co(III) 6 8.2 89 0.092
Cr(III) 6 8.2 94 0.087
Fe(II) 4 8.2 146 0.056
Fe(II) 6 13.8 181 0.076
Fe(III) 4 78
Fe(III) 6 8.2 99 0.083
Ga(III) 4 76
Mn(II) 6 13.8 194 0.071
Mn(II) 8 16.4 231 0.106
Mn(III) 6 8.2 100 0.082
Ni(II) 6 13.8 159 0.087
U(IV) 8 8.2 122 0.067
V(III) 6 8.2 99 0.083
W(IV) 6 76
W(VI) 4 41
W(VI) 6 46
Zn(II) 4 8.2 139 0.059
Zn(II) 6 13.8 171 0.081
Zr(IV) 6 2.7 83 0.033

volume is reached almost spontaneously above
the glass transition temperature. Lowering the
temperature and hence increasing the viscosity
result in a point being reached at which the vol-
ume relaxation time becomes at least as large
as the observation time. The cooling glass body
does not reach its equilibrium geometry, and a
volume change is observed as a result. Thus care
must be taken in cooling larger glass bodies to
obtain a final product with acceptable low stress.
The feasibility of glass-to-glass or glass-to-
metal seals depends, apart from interfacial ten-
sion, on the absence of glass reboil and degassing
of the metal at the sealing temperature, and on
the thermal expansion mismatch of the two ma-
terials. For glass-to-glass sealing with accept-
able reduced strain, the difference in thermal ex-
pansion coefficient generally should not exceed
ca. 3×10−7 K−1 .
The production of glass-to-metal seals is
complicated by the substantially larger linear
thermal expansion of steel, which varies bet-
ween 130×10−7 K−1 for unalloyed steel and
160×10−7 K−1 for stainless steel. Conditions
34 Glass
are relatively simple if thin metal sections are
used or if the seal is a so-called compression seal,
where the higher expansion metal surrounds the
glass and, after cooling, keeps the glass in com-
pression.
Two properties must be controlled to ensure
proper glass-to-metal seals. The first involves
a complicated and rigorously controlled oxida-
tion – reduction at the interface to form a good
bond; the second involves matching the thermal
expansion of the glass with that of the metal. The
latter causes no problems as long as the glass
adjusts to any thermal expansion mismatch by
viscous flow. The system must be designed so
that below the set point, thermal contractions of
the glass and the metal are similar in magnitude
and mismatches are taken up preferentially by
the metal.
4.5. Elastic Properties
Two classes of variable suffice to describe the
mechanical properties of glass: (1) elastic vari-
ables and (2) mechanical strength. An elastic
material has the ability to recover size and shape
after deformation. An ideal elastic material de-
forms instantaneously when subjected to stress,
and the deformation recovers instantaneously
when the stress is removed. Elasticity is mea-
sured as Young’s modulus E, which is defined
as the ratio between linear stress and collinear
strain for a rod or bar, or as bulk modulus K, if a
uniform compressive stress is applied to a body.
The compressibility K is the inverse of the com-
pressive stress. Measurement of the elastic mod-
ulus on annealed samples is described in ASTM
C 623-71 (1981) and entails testing the deforma-
tion of a material in the direction of the applied
force.
E =σ/ε
Here E is the proportionality constant bet-
ween applied stress, σ, and the resulting strain,
ε. The ratio of the resulting lateral stress to the
applied longitudinal stress is the Poisson ratio
σ. For shear stress, the proportionality constant
is the shear modulus G. The relation of Young’s
modulus E, bulk modulus K, shear modulus G,
and Poisson ratio σ is as follows:
E = 3K (1 − 2σ) = 2G (1+σ)
Glasses are perfectly elastic: the deformation
is directly proportional to the applied stress, in-
dependent of loading rate, until failure. A high-
modulus glass is one in which the atoms are
closer together or the bonds are stronger and
hence more resistant to deformation. Vitreous
silica has an elastic modulus of about 72.9 GPa,
a shear modulus of 31.3 GPa, and a Poisson ratio
of 0.165. Below ca. 1273 K it is close to an ideal
elastic body under most loading conditions. It
deforms instantaneously, does not creep (i.e., de-
form slowly under continuous load), and recov-
ers instantaneously on removal of the load. In-
troduction of alkali in vitreous silica decreases
the connectivity and hence the elastic modu-
lus. Some elastic constants for alkali silicate and
other glasses are collected in Table 18.
The modulus can again be increased by
adding network formers (e.g., B2 O3 or Al2 O3 )
to alkali silicate glasses, as illustrated in Table 16
for the sodium – alumina – silica system. Sim-
ilar results can be obtained by adding oxides
(e.g., CaO, MgO, La2 O3 , or ZrO2 ). Relatively
high moduli are encountered in alkaline-earth
aluminosilicate glasses, with values as high as
118 GPa. Elastic moduli normally tend to de-
crease with increasing temperature and increase
with increasing pressure, approaching zero only
above the glass transition temperature.
Vitreous silica, Pyrex, and some other
glasses with low modifier concentrations, be-
have anomalously: the elastic modulus increases
with increasing temperature. The rationalization
for this is the uncommonly small thermal expan-
sion coefficient of the Si−O and B−O bonds,
which have thermal expansions of zero between
296 and 1273 K.
4.6. Mechanical Strength
The theoretical strength of a glass is extremely
high (> 104 MPa) when the energy required to
break chemical bonds is calculated. In practice,
however, measured strengths are much lower
and vary widely. Typical values are ca. 104 MPa
for glass fibers, 102 MPa for flame-polished
silica rods, and 7 × 103 MPa for thin-walled
freshly drawn glass. The reason for the discrep-
ancy between theory and practice, as well as the
 Glass 35
Table 18. Elastic constants of silicate glasses [74]

Composition, mol % E, GPa G, GPa K, GPa σ

20 Li2 O · 80 SiO2 76.99 31.40 46.81 0.226

20 Na2 O · 80 SiO2 61.08 25.18 35.46 0.213
20 K2 O · 80SiO2 49.04 19.75 31.62 0.242
20 Cs2 O · 80 SiO2 37.67 14.86 27.02 0.274
20 Na2 O · 20 Al2 O3 · 60 SiO2 73.2 30.6 40.13 0.196
30 PbO · 70 SiO2 50.13 21.35 25.63 0.174
25 MgO · 25 CaO · 50 SiO2 99.14 38.81 74.11 0.277
25 MgO · 25 BaO · 50 SiO2 79.52 30.97 61.24 0.284

scatter in data, is the inclusion of many surface
and internal flaws that act as stress concentra-
tors or risers. Fracture is usually in the tensile,
as opposed to the compressive, mode due to this
type of stress concentration. The useful strength
of glass articles is, therefore, only a fraction of
the theoretical value.
The susceptibility of glass to stress corrosion
additionally reduces the practical strength of a
glass article by a further 30 % in long-term us-
age. In building construction, the maximum al-
lowable tensile load on a soda lime glass is 7.0 Pa
under sustained loading (at least 1000 h). The
chemical composition of glass has a significant
effect on its design strength. The allowable stress
for glasses with greater resistance to stress cor-
rosion (e.g., fused silica) can be twice as high as
that for soda lime glass.
Plastic deformation of glass is prevented by
its high viscosity at room temperature, combined
with the absence of slip planes. Broken bonds re-
sulting from excessive stress tend not to anneal
but function as nucleation sites for cracks, unless
enough time passes for rounding of the tips due
to aging or zero stress corrosion. If the crack
grows, the stress intensity concentration at the
tip increases. Those bonds that were intact will
break, causing glass fracture.
Glass can be made more load-resistant in sev-
eral ways: The number of surface flaws can be
reduced, by careful handling, annealing after
forming, or acid etching. The highest-strength
common glass articles are optical waveguide
fibers that remain untouched until a coating
which protects the fibers from mechanical abuse
is applied. Secondary treatment, such as ion ex-
change, thermal tempering, glazing, differential
crystallization, or layering, can induce compres-
sive stresses on the surface of the glass which
must be overcome before surface stress reaches
the necessary tensile stress that leads to fracture.
4.7. Hardness
Glass hardness is tested in one of three ways:
scratching, grinding or abrasion, and penetra-
tion. Results obtained with these methods, can
be correlated to some extent. However, the hard-
ness sequence for a series of glasses may de-
pend on the method. The most commonly used
is Knoop hardness, measured with a diamond
pyramid indenter. Historically, Moh’s scale of
scratch hardness has been employed. On this
scale, glass hardness lies between that of the cal-
cium phosphate apatite, with a hardness of 5, and
quartz, with a hardness of 7. Common materi-
als that are hard enough to scratch glass include
diamond, agate (amorphous SiO2 ), sand, silicon
carbide, hard steel, and emery. Glass itself can
be used as an abrasive.
4.8. Thermal Properties
Heat transfer and transport in melts and glasses
are important variables in the design and con-
trol of material processing at elevated temper-
ature. They occur in two ways in rigid glass:
conduction and radiation. In a glass melt convec-
tion also transports heat. In dielectric (i.e., po-
larizable) materials, two independent modes of
heat transfer operate: thermal (phonon) conduc-
tion due to lattice wave propagation, and radia-
tive (photon) conduction due to absorption and
reradiation of electromagnetic energy. At low
to moderate temperature, the transfer of thermal
energy occurs primarily by phonons; at elevated
temperature, heat transfer by photons predom-
inates. Knowledge of heat transfer is essential
36 Glass

in growing crystals from semitransparent melts where  is the resistivity, a is the cross-sectional
and in melting, annealing, and forming glasses. area perpendicular to the direction of current
Heat-transfer values are also an important pre- flow, and l is the length of the sample. Elec-
requisite for the construction of furnaces, molds, trical conductivity is defined as the inverse of
and energy balances in glass technology. resistivity. Log  is reported at 523 and 623 K
Thermal conductivity is measured in watts for comparative purposes and to establish tem-
per meter per degree; the room tempera- perature dependence.
ture thermal conductivity of glass is 0.67 –
1.38 W m−1 K−1 . Common glass compositions
have thermal conductivity values near the upper
end of the range. Conductivity increases by ca.
25 % from room temperature to 473 K. Radia-
tive heat transfer appears in clear glasses around
800 K and becomes the major source of heat
transport at higher temperature. Vitreous silica
has the highest thermal conductivity at room
temperature (1.38 W m−1 K−1 ), and high lead
silicate glass has the lowest (0.71 W m−1 K−1 ).
For Corning Code 7740, a Pyrex brand glass, the
thermal constants are as follows: thermal con-
ductivity (298 K), 0.96 W m−1 K−1 ; mean spe-
cific heat (298 – 448 K), 0.84 J g−1 K−1 ; thermal
diffusivity, 0.56 mm2 s−1 ; and emissivity coef-
ficient, 0.94.
The common heat capacity of glass at room
temperature is ca. 0.837 J g−1 K−1 . Glasses that
contain atoms of high atomic mass show some-
what lower specific heats (e.g., 0.5 J g−1 K−1 for
a 50 wt % PbO – silicate glass). The specific heat
increases slightly with increasing temperature,
e.g., for vitreous silica: 0.73 J g−1 K−1 at 298 K;
1.12 J g−1 K−1 at 773 K; and 1.21 J g−1 K−1 at Figure 20. Volume resistivities for some industrial glasses
1273 K. An average value of 1.05 J g−1 K−1 in a) Glass no. 8058; b)Glass no. 0080; c) Glass no. 7740;
the region 273 – 873 K is typical. d) Glass no. 7900; e) Glass no. 7070; f) Glass no. 7040;
g) 33 CaO · 67 B2 O3 ; h) Glass no. 9753

4.9. Electrical Properties The electrical conductivity at room temper-

Electrical conductivity in industrial glasses is as-
sociated with the transport of ions. The temper-
ature dependence of electrical conductivity in
glasses is positive; conductivity increases with
increasing temperature. This property of glass is
useful in electrical engineering, where low con-
ductivity is required at ambient temperature, and
in electric melting of glass, in which corrosion-
resistant electrodes are submerged in the melt
and the relatively low electrical resistance of the
melt itself at high temperature is used. Electrical
resistance R, is defined by the following equa-
tion:
ature for common silicate glasses is 10−10 –
10−11 Ω−1 cm−1 , indicative of their good insu-
lating properties. Glass can be used as an elec-
trical insulating material (→ Insulation, Elec-
tric). The value T K=100 is the temperature at
which a glass has a specific conductivity of
10−8 Ω−1 cm−1 . For window glass, which is not
a particularly good electrical insulator, this tem-
perature is between 423 and 473 K. Water layers
on the surface of glass at low temperature may
increase surface electrical conductivity by a fac-
tor of 103 . Some examples of volume resistivity
are shown in Figure 20.
R=l/a
 Glass 37

In highly connected liquid oxides such as

B2 O3 , GeO2 , and SiO2 , electrical conductivities B
are typically <10−5 Ω−1 cm−1 at the melting
point, consistent with the high viscosity. Melts
of network-modifying oxides, on the other hand,
have low viscosity (<0.05 Pa · s) and high spe-
cific conductivity (>1 Ω−1 cm−1 ) at the melt-
ing point, indicating dissociation into Mn+ and
O2− ions. Most of these molten oxides have
higher conductivities than molten salts, indicat-
ing that both electron conduction and ion con-
duction occur. This is particularly true when the
metal atoms have a variable valence (e.g., Fe2+
and Fe3+ in liquid iron oxide). A characteristic
of ionically conducting melts is that their spe-
cific conductivity increases sharply on fusion,
in contrast to melts that conduct by means of
electrons.
Specific conductivity in melts depends on the
type and amount of alkali ions present. Some ex-
amples are given in Table 19.
Table 19. Electrical conductivity of molten alkali borates and
silicates
R2 O, mol % Conductivity, Ω−1 cm−1
10 Li2 O · 90 B2 O3 0.051 (1273 K)
10 Na2 O · 90 B2 O3 0.045 (1273 K)
10 K2 O · 90 B2 O3 0.040 (1273 K)
Li2 O – SiO2 a 1.7 – 6.3 (1773 K)
Na2 O – SiO2 b 0.64 – 1.8 (1773 K)
K2 O – SiO2 c 0.40 – 1.1 (1773 K)
a
Li2 O 33 – 58 mol %.
b
Na2 O 19 – 34 mol %.
c
K2 O 18 – 34 mol %.
Mixtures of alkali-metal oxides in sili-
cate, borate, or phosphate glasses give rise
to anomalously low electrical conductivi-
ties. This effect, which is not well under-
stood, is called the mixed alkali effect. An
example is the specific conductivity of a
Na2 O · K2 O · 4 SiO2 glass (10−12 Ω−1 cm−1 )
which is much smaller than that of ei-
ther Na2 O · 2 SiO2 glass (10−8 Ω−1 cm−1 ) or
K2 O · 2 SiO2 glass (10−9 Ω−1 cm−1 ). This ef-
fect is not limited to cations such as alkali met-
als but also occurs with anions (e.g., halides).
In this case, it is called the mixed halide effect.
This effect has been characterized in lead silicate
glasses [112].
The temperature dependence of electrical
conductivity is given by the relation:
log (1/) =A −
T
The activation energy for charge transport is
lower above the glass transition temperature.
The activation energy E for alkali-metal sil-
icates is 35 – 50 kJ and is virtually indepen-
dent of composition or type of cation present.
For alkali-metal borates, the activation energy
is about twice as large. The activation energy
for alkaline-earth silicates is about 180 kJ at
20 mol % R2 O and decreases to about 85 kJ at
60 mol %, values similar to those found in borate
melts. For iron, manganese, and lead silicates, E
is about 40 kJ lower than for alkaline-earth sil-
icates. For all these silicate melts, E is about
40 kJ lower than the activation energy for vis-
cous flow. This activation energy is determined
by measuring the temperature dependence of the
melt viscosity.
The static dielectric constant represents the
ratio of the energy of the electric charge stored
between two metal plates with the material as in-
sulator to the energy of the electric charge stored
between the same plates with vacuum as insu-
lator. The magnitude of the dielectric constant
depends on the polarizability of the glass con-
stituents. Pure vitreous silica, with its very low
polarizability, has a dielectric constant of 3.7.
High lead glasses can have a dielectric constant
at ca. 15, and specialty glasses with high PbO,
BaO, or TiO2 content have a dielectric constant
of ca. 60. The numerical value of dielectric con-
stant can be estimated for most industrial glasses
(except for vitreous silica) by using the empiri-
cal formula:
Dielectricconstant = 2.2 × density
where the density is expressed in grams per cu-
bic centimeter.
The dielectric loss, a dissipative factor, is a
measure of the deviation of a material from an
ideal dielectric. Generating an electric field in an
insulating material introduces a specific quantity
of electrical energy. If this energy is partially
recoverable, the material is called a dielectric.
The irrecoverable part of the energy is lost as
heat. The ratio between irrecoverable and re-
coverable energy is called the dielectric loss. At
least three types of dielectric loss can be distin-
guished: resonance vibrational losses, migration
losses caused by mobile ions, and deformation
38 Glass

losses related to defects in the silicon – oxygen

network.
Dielectric loss depends strongly on fre-
quency. Conductivity and relaxation losses dom-
inate at low temperature. The influence of com-
position on energy loss in this temperature re-
gion is comparable to that observed for electri-
cal conductivity. Dielectric losses have a min-
imum value at room temperature in the range
of 106 – 108 Hz. Losses for common glasses
in this frequency range vary between 10−2
and 3×10−2 . Dielectric loss can be lowered to
<10−3 (106 Hz, 298 K) in specialty glasses, usu-
ally PbO – BaO rich or mixed alkali borosilicate
glasses. Vitreous silica has still lower loss.
Dielectric failure may be due to discharge or
arcing, thermal failure, or intrinsic breakdown.
In thermal failure, electric losses within the di-
electric raise its temperature, which in turn in-
creases the losses and flow of current. Break-
down occurs when this cumulative action results
in instability. Intrinsic breakdown is associated
with defects and voids in the glass. The intrin-
sic dielectric strength of glass is high, e.g., for
silica, borosilicate, soda lime, and lead – alkali,
values are 5000, 4800, 4500, and 3100 kV /cm
(d.c.), respectively, for thin sections.
4.10. Gas Permeability
The permeability of glass to gas is important
in high-intensity tungsten – halogen lamps. The
glass must be able to withstand leakage of pres-
surized halogen at elevated temperature. The
volume of gas that permeates through glass is
directly proportional to the time of exposure, the
area of the glass, and the difference between am-
bient and gas pressure, and is inversely propor-
tional to the thickness of the glass:
ktAp
V=
l
where t is time, A is area, p is pressure, l is thick-
ness, and k is a constant. The constant of pro-
portionality k is thus given by the equation:
Vl
k=
tAp
Figure 21. Dependence of gas permeation upon temperature
for 96 wt % SiO2 glass (Corning code 7900)
The constant of proportionality, k, is plotted as a function of
the temperature.
a) Oxygen; b) Neon; c) Hydrogen; d) Helium∗ Value of k
when V is in cubic meters, l in meters, t in days, A in square
meters, p in 1015 Pa.
4.11. Chemical Stability and Surface
Properties
The chemical stability of a glass depends on its
chemical composition and on the medium with
which it is in contact. The solubility of amor-
phous silica is illustrated in Figure 22 and of
alumina, a typical amphoteric element soluble
in both acids and bases, in Figure 23. Such am-
photeric solubility behavior is commonly deter-
mined by the ability of an element to change
its coordination state as a function of pH. Thus,
in the case of alumina, the prevailing solu-
tion species at high pH has aluminum coor-
dinated tetrahedrally to four hydroxyl groups
[Al(OH)4 ]− . At low pH, the prevailing solu-
tion species is an aluminum atom surrounded
octahedrally by water molecules, Al(H2 O)3+ 6 .
If these coordination changes are considered as
a function of pH, the formation of zeolites con-
taining only fourfold oxygen-coordinated alu-
minum atoms in neutral or alkaline environment
is certainly no coincidence, whereas clay miner-
als with sixfold oxygen-coordinated aluminum
atoms are always formed in an acidic environ-
ment.

Gas permeation is also strongly dependent on

temperature, as is shown by plotting k as a func-
tion of temperature (see Fig. 21).

Figure 22. Solubility of amorphous SiO2 as a function of pH [113]
a) Insolubility domain; b) Stable multimeric domain; c) Mononuclear wall; d) Mononuclear domainSolution NMR shows that
silica speciation at high silica concentration is more extended than indicated here [67]. At low silica concentration and neutral
pH silica dimers occur [114]. The mononuclear wall (dashed line) and mononuclear domain indicate the region in which
mononuclear silicon species occur, as shown by potentiometry.
Figure 23. Solubility of amorphous Al2 O3
The numbers represent the x and y values for a specific solu-
tion species. 27 Al solution NMR shows fewer species than
indicated in this diagram [103], [104].
The solubility behavior of alkali-metal alumi-
nosilicate glasses can be inferred qualitatively
from that of silica and alumina. A review of
glass – water interactions and solubility has been
published [115].
Vitreous silica is soluble to about 100 ppm in
acidic or neutral solution (Fig. 22). The corro-
sion of alkali silicate glasses in such solutions in-
volves an exchange between alkali-metal atoms
and protons in a diffusion-controlled process.
The silica framework is thought to remain intact
and is presumed to form a silica gel-like pro-
tective surface layer. Only in leaching with hy-
drofluoric acid or concentrated phosphoric acid
is the silica framework itself attacked. In a diffu-
Glass 39
sion controlled process such as the alkali-metal
atom enchange, the rate of dissolution decreases
as the square root of time during glass leaching.
The temperature coefficient of glass leaching
reactions increases by a factor of ca. 1.5 for ev-
ery 10◦ increase in temperature. Increasing the
network-former content or doping with multi-
valent cations strengthens the network. Next to
vitreous silica, borosilicate and aluminosilicate
glasses have the best acid resistance. No protec-
tive gel coating is formed during acid leaching
of phosphate or borate glasses; therefore, these
glasses are not very resistant to acidic solution.
Alkaline attack involves dissolution of the
glass framework and formation of anions of
silicic acid. Glasses strengthened with CaO,
MgO, Al2 O3 , or B2 O3 increase corrosion re-
sistance against bases. The most corrosion-
resistant glasses are those with substantial ZrO2
content.
Glass corrosion can be used to advantage.
One industrially important class of materials
consisted of the soluble silicates. These are
solutions with a viscosity on the order of
1 mPa · s, manufactured by dissolution primar-
ily of sodium or potassium silicate glasses in
pressurized steam. A review of their industrial
uses is given in [116].
40 Glass
Water dissolution can be considered a com-
bination of acid and base attack. First, the pH
of the water increases by inclusion of protons in
the glass network at the expense of alkali metal;
this is followed by attack of the network in the
resultant basic environment. Base attack plays
a particularly prominent role in glasses because
of daily fluctuations in climate. Morning dew
causes proton – alkali metal exchange, followed
by an increase in alkali-metal concentration on
evaporation, which enhances attack by alkali.
For industrial purposes, weathering is defined
as corrosion by atmospheric-borne gases and va-
pors, such as water or carbon dioxide. The acid
resistance of glasses is classified by their behav-
ior in 5 % hydrochloric acid at 368 K (95 ◦ C) for
24 h.
Metal or metal halide attack on silica glass at
elevated temperature is especially important in
light-bulb production. Reaction between vitre-
ous silica and various metals or halides occurs at
elevated temperature. Thus, although alkali met-
als stain glass only at relatively low temperature
(<573 K), severe induced devitrification can oc-
cur at higher temperature (ca. 1173 K); with at-
tendant glass failure. A 1-h exposure of silica
tubes to sodium vapor below 1273 K causes fail-
ure due to devitrification. Other elements that in-
duce devitrification at 1523 – 1623 K are Mn, Sn,
Fe, and Zn. Metal halides that react with vitre-
ous silica below 1473 K are LiCl, NaCl, SnCl2 ,
NaBr, and KBr. At 1473 – 1673 K, RbCl, CsCl,
NaI, KI, MgCl2 , CaCl2 , BaCl2 , and AlCl3 cause
failure.
Surface Properties. The acid-base proper-
ties of glass surfaces in aqueous solution depend
on the point of zero charge (pzc), i.e., that pH at
which the surface is not charged. The surface is
positively charged if the pH is lower than the
pzc, and negatively charged if the pH is higher.
The reason for this change in surface charge is
that metal oxide surface chemistry in water is
dominated by the following reactions [117].
MOH+
2 −→ MOH + H
+
pK1
MOH −→ MO− + H+ pK2
Here M represents a surface metal ion and OH
is the surface hydroxyl exposed to the medium.
The two reactions indicate that a positive surface
charge is associated with Bronstedt acidity (pro-
ton donor) whereas a negative surface charge is
associated with Bronstedt basiscity. The point of
zero charge (pzc) is the average of the two pKs:
pK1 +pK2
pzc =
2
Some typical values are shown in Table 20.
Table 20. Values of pK1 , pK2 , and pzc for some oxides
Oxide pK1 pK2 pzc
Silica −2.77 6.77 2.0
Alumina 7.70 9.30 8.5
Titania 5.40 6.40 5.9
Goethite, FeO(OH) 6.99 8.40 7.7
As might be anticipated, a relation between
the point of zero charge and cationic field energy
can be constructed [118]. High field energy is
associated with a pzc at low pH, and low field
energy with a pzc at high pH.
The importance of the pzc’s of oxides for
glasses lies in the fact that pzc’s for crystalline
and amorphous materials are similar. The pzc’s
of glasses can therefore be estimated from the
pzc’s of their constituent oxides. For example,
the pzc of quartz occurs at a pH of 2, and the
pzc’s of the high-silica glasses Pyrex, Vycor, and
silica glass occur at a similar pH.
The minimum rate of dissolution of crys-
talline silicas occurs at their pzc (i.e., pH 2)
[119]; this is of importance in adjusting glass
compositions for maximum durability.
4.12. Optical Properties
Light transmission, absorption, reflection, and
scattering describe the macroscopic aspects of
light – glass interaction. The optical properties
of glasses can be characterized simply and un-
equivocally by the spectral transmittance τλ as a
function of wavelength λ of the irradiating light.
Spectral transmittance is the ratio of the light
flux Φd leaving the glass to the light flux Φ of
monochromatic light radiation:
τλ =Φd /Φ
The incident light flux can be partitioned over
three light – glass interactions:
Φ=Φ +Φa +Φd
where Φd is the transmitted flux, Φa the absorbed
flux, and Φ the reflected flux.

4.12.1. Transmission, Absorption, and
Reflection
Light is in part reflected, absorbed, and transmit-
ted. Absorption of light requires the operation
of an absorption mechanism in the glass. Visi-
ble light absorption usually occurs by excitation
of electrons from the valence to the conduction
band and often results in a change of color of the
glass.
The total transmission of a glass is deter-
mined by reflection at the glass surfaces and op-
tical absorption in the glass. Neglecting multi-
ple reflections between the glass surfaces, the
total transmission in air of a flat sample at a
specific wavelength is approximately equal to
(1 − R)2 e−βt where β is the absorption coef-
ficient, t the thickness of the glass, and R the
air – glass reflection coefficient. Transmission
is a function of wavelength. The lower wave-
length transmission limit in ultrapure silica is ca.
150 nm in the ultraviolet. The upper wavelength
transmission limit occurs at 5000 nm in the far
infrared due to excitation of vibrational states.
The lower transmission limit occurs in practice
at only ca. 2700 nm because of the ubiquitous
presence of water in vitreous silica.
Transmission can be controlled by the type
of glass (e.g., silicate, phosphate, or borate) or
by the control of coloring additives, oxidizing
or reducing melting atmosphere, melting tem-
perature, and cooling schedules. Diffuse trans-
mission occurs in glasses that contain suspended
particles (e.g., opal glasses).
Reflectance depends strongly on the qual-
ity of the glass surface, the angle of incidence,
the indices of refraction of the glass and the
surrounding medium, and the wavelength. Re-
flectance can be specular, as in polished or
precision-molded surfaces, or diffuse for ground
or irregularly etched ones. The fraction of light
of normal incidence reflected by a single plane
surface is given by
R= [(n−1) / (n+1)]2
in which n is the refractive index of the glass
at the wavelength of interest (if the refractive
index of air is assumed to be 1). Reflectance
loss at normal incidence for simple soda lime
glasses is about 4 % per surface, so that 92 % of
the incident light is transmitted by a perfectly
Glass 41
clear soda lime glass. Glass with a higher index
of refraction transmits less light. Thus, glasses
with a refractive index of 1.7 and 1.9 transmit
87 and 81 %, respectively, of the incident light.
Low-index coating or special surface treatment
of glass may significantly reduce losses due to
reflection.
4.12.2. Refractive Index, Dispersion, and
Optical State
The most important characterizations of an opti-
cal glass are refractive index and Abbe number.
The refractive index of a glass is defined as the
ratio of the velocity of light in a vacuum to that
in the glass; larger refractive indices, therefore,
indicate lower velocity of light in the material.
Refractive index depends on wavelength, so
that values are reported with the wavelength
employed. Wavelengths commonly used are the
yellow helium D line at 587.6 nm, the green mer-
cury line at 546.1 nm, and the yellow sodium D
line at 589.29 nm. The refractive index is gener-
ally measured against air, although the refrac-
tive index of air is defined against a vacuum
(nair /nvac = 1.00023). Refractive indices are usu-
ally between 1.46 (amorphous silica) and 1.97
(lead silicate glass). Some exotic glasses reach
a refractive index exceeding 2.0. Comparison
of refractive index variations of amorphous and
crystalline silicas and alkali silicate glasses sug-
gests that intra-orbital charge transfer on the
oxygen atom, i.e., variation in bonded and non-
bonded electron density on the oxygen atom
(Fig. 24), are primarily responsible.
The refractive index is proportional to the
square root of the number density of dipole oscil-
lators in a material. Thus, the refractive index of
amorphous and crystalline silica increases sys-
tematically with increasing density (see Fig. 25).
Changes in the electronic structure of silica oc-
cur concomitantly with density variations, as can
be seen from variations in the 29 Si MAS NMR
chemical shifts. These chemical shift variations
result from changes in s electron density at the
silicon nucleus (Fig. 26). Thus, the charge on
oxygen and silicon in silica varies as a function
of density. On the other hand, oxygen 1 s photo-
electron spectroscopy indicates that the overall
electronic charge on oxygen is − 0.74 for vitre-
ous silica, quartz, and cristobalite. This similar-
42 Glass
Figure 24. Change of molecular orbitals into atomic orbitals
of silicon and oxygen in a Si−O−Si bond [79]
ity in charge on oxygen and, therefore, silicon in
crystalline and amorphous silicas suggests that
a more subtle variation in electron density is re-
sponsible for chemical shift and polarizability
variations in silicas.
One subtle variation in electron density in
Si−O bonds is associated with shifts in the
bonding and nonbonding electron density on the
oxygen atom as a function of Si−O−Si angle.
Hartree – Fock calculations on H6 Si2 O7 show
that although the overall charge on oxygen does
not vary as a function of the Si−O−Si angle, the
ratio of nonbonded to bonded electron density
decreases with decreasing Si−O−Si angle from
1.44 (180◦ ) to 1.07 (120◦ ). This shift in electron
density accounts for the increased polarizability
of the oxygen atom and for the observed shift of
Figure 25. Variation in refractive index as a function of den-
sity for silica
a) Lechatelierite, a natural amorphous silica; b) Tridymite;
c) Cristobalite; d) Keatite; e) Quartz; f) Coesite; g) Stishovite
the 29 Si MAS NMR resonances to lower field
with smaller Si−O−Si angle.
The density of a glass and its refractive in-
dex are not necessarily coupled with one an-
other. Plots of density versus refractive index of
20 mol % alkali silica glasses (Fig. 27) show that
no clear cause and effect relation between these
two variables exists. The reason for the absence
of such a relation in the alkali silica glasses pre-
sumably lies in the increase in Si−O−Si angle
with higher atomic mass alkali atoms, hence de-
creasing the number density of oscillators with
increasing glass density. Alternatively it can be
argued that larger Si−O−Si angles decrease the
oxygen polarizability, hence accounting for the
observed refractive index behavior. The crys-
tal structures of the heavier alkali silicates have
not yet been determined. Hence, such increase

Figure 26. Variation in 29 Si chemical shift as a function of
Si−O−Si angle [66]
The chemical shift is related to the Si−O−Si angle by
the following formula: δ (ppm) = − 19.8215 − 0.608526
Si−O−Si
in Si−O−Si angle with heavier alkalis in crys-
talline alkali silicates is still a matter of conjec-
ture [120].
Optical glasses are usually described in terms
of refractive index at the sodium D line, nD
589.3 nm, and ν value (Abbe number). The
Abbe number is calculated from the relation
ν = (nD −1) / (nF −nC )
in which nF and nC are the refractive indices
at the hydrogen F (486.1 nm) and C (656.3 nm)
lines, respectively. The difference nF − nC is the
average dispersion, and its reciprocal 1/ν is the
relative dispersion. Materials with high disper-
sion have Abbe values around 30; those with low
dispersion, around 80.
The refractive index and the Abbe number
are incorporated by Schott Glass into a six-
digit numbering system used to identify opti-
cal glasses. Common spectacles are designated
523 – 586, i.e., nD = 1.523 and ν = 58.6.
Crown glasses have nD < 1.60 and ν ≥ 55.
They are usually alkali silicate glasses. Glasses
such as alkali lead silicate glasses with ν < 50
are designated flint glass. The Schott nomen-
clature for optical glass is used in Figure 28.
Labeled areas represent commercially available
glass.
When nD and ν are identical for glasses with
regular dispersion properties, the rule holds that
the remaining dispersions are also identical. For
standard glasses, the complete refraction behav-
Glass 43
Figure 27. Variation in refractive index with density for
20 R2 O – 80 SiO2 silicate glasses
ior can, therefore, be determined from these two
variables.
Refractive index and dispersion depend on
the structure and constituents of the glass and
on their interaction with light. Like most other
glass properties, partial molar refractive index
coefficients have been calculated.
Measurement of refractive index, although
generally requiring some grinding and polishing
of the sample, can be carried out with precision
and with reasonable speed; it is, therefore, used
in quality control to determine the homogene-
ity of the glass. Dispersion and Abbe number
are used mainly to characterize optical and oph-
thalmic glasses.
4.12.3. Temperature Dependence of
Refractive Index
The density of glass and the UV absorption edge
vary with temperature. Both effects influence
the refractive index, causing in some glasses
a negative, and in others a positive, tempera-
ture coefficient. Athermal glasses, which do not
change their refractive index in specific temper-
ature ranges, are available.
4.12.4. Stress Optical Coefficients
Glass becomes birefringent when strained.
Stress and strain are proportional to each other in
44 Glass

Figure 28. Refractive index vs. dispersion and optical classification of glasses
Shaded area indicates region of glass formation. Plexiglass is a methyl methacrylate resin, lucite is an acrylic resin. BaF =barium
flint; BaK = barium crown; BaLF = light barium flint; BaSF = heavy barium flint; BK = borosilicate crown; F = flint;
FK = fluorocrown; K = crown; KF = crown flint; LaF = lanthanum flint; LaSF = heavy lanthanum flint; LaK = lanthanum crown;
LF = light flint; LLF = very light flint; PK = phosphate crown; PSK = heavy phosphate crown; SF = heavy flint; SK = heavy
crown; SSK = very heavy crown; TiF = titanium flint

glass. The stress optical coefficient B, or Brew- 4.12.5. Radiation Effects

ster’s constant, expresses the relationship bet-
ween optical retardation produced in a beam of
plane-polarized light as it passes through a glass
and the imbalance between principal stresses
that exist along the path of this light beam. Brew-
ster’s constant is the ratio between retardation
R (in nanometer path difference per centimeter
path) and stress F (in kilograms per square mil-
limeter)
B =R/F
The stress optical coefficients vary greatly with
glass composition. The value of B ranges from
ca. − 1 for extra-dense flint containing 80 % PbO
to ca. 2.5 for soda lime glass, ca. 3.4 for 96 %
silica glass, 7 for epoxy resin, and 2000 – 14 000
for gelatin.
The changes occurring in silicate glass under the
action of ionizing radiation (e.g., high-energy
electrons, gamma-rays, X-rays, or combinations
of these) tend to be the same in both the nature
of the excitation process involved and the degree
of defect formation. This is true at saturation as
long as the same amount of material absorbs the
same amount of radiation energy (the energy ap-
proximation). Mass absorption coefficients for
X-rays are, however, substantially higher than
those for 137 Cs and 60 C gamma rays with ener-
gies of 0.66 and 1.17 MeV, respectively. Defect
saturation will, therefore, proceed much faster
with X than with gamma rays. Color changes
induced by sunlight are commonly referred to
as solarization.
The stability of glass in a flux of neutrons
depends in particular on the amount of boron,
which possesses a high absorption coefficient for
neutrons. Boron-free glass can generally with-
 Glass 45

stand a flux of 1019 neutrons/cm2 . Ion bombard- Limiting wavelengths (lower wavelength
ment disrupts the glass structure, producing dis- limit) of absorption for some oxide and fluoride
coloration and free oxygen. The effective life- glasses are given in Table 22. Clearly, in absence
time of electronic tubes can be affected consid- of impurities that absorb light in the visible re-
erably by reaction between free oxygen and the gion, none of these glasses shows coloration be-
cathode. cause no absorption extends beyond 400 nm.
Electron browning affects the performance of
Table 22. Limiting absorption wavelength for various oxide and
cathode-ray tubes containing oxides of lead or fluoride glasses
bismuth. These compounds are easily reduced
Glass type Absorption Energy,
by the incident electrons, producing a brown tint wavelength eV
in the glass. λT, nm a
Relatively low doses of gamma rays tend
P2 O 5 <150 b >8.3
to discolor dense lead silicate glasses. Among SiO2 162 7.7
amorphous oxides, ultrapure vitreous silica is B2 O3 200 6.2
most resistant to discoloration. The drawbacks HPO3 273 4.5
GeO2 363 3.4
of vitreous silica are its low density and the P2 O5 – R2 O (R = alkali metal) 220 5.6
expense of production. Alternatives are glasses SiO2 – R2 O 270 4.6
with intermediate density to which oxides with B2 O3 – R2 O 360 3.4
variable cation valence are added: Ce3 O4 (Ce3+ , BeF2 c 90 13.8
ZBLA c 210 5.9
Ce4+ ) is commonly used as such an oxide be-
a
cause of its effectiveness in increasing color sta- b
Position of UV edge at 50 % transmission.
Difficult to measure because of the ubiquitous presence of
bility. Lead silicate glass combined with inter- water.
mediate density, cerium-doped glass is used in c
Data from [93], [122], [123].
composite windows with remarkable resistance
to radiation damage. They are used, for instance, Transmission curves for some simple uncol-
in environments with relatively high-intensity ored glasses are shown in Figure 29. The UV
radiation fluxes, matching the absorption char- absorption is of principal importance. This ab-
acteristics of heavy concrete used for shielding sorption arises from the energy absorbed by elec-
walls. trons excited from the valence to the conduction
Cobalt-containing glasses have been devel- band as shown in Figure 30. The occupied states
oped for their radiation sensitivity. More sensi- are the valence band and the empty states are
tive silver phosphate glasses are used as dosime- the conduction band; the energy difference bet-
ters to measure exposure to X– or gamma rays. ween the two is the band gap. More sophisticated
analyses have been made [121].
4.13. Color of Glasses
White light is composed of a mixture of col-
ors, the different colors representing a spectrum
of frequencies and hence of energies. The rela-
tion between wavelength, frequency, and energy
is given in Table 21. The human eye is sensitive
to light of frequency (3.9 – 7.5)×1014 Hz, corre-
sponding to a wavelength of 400 – 760 nm and an
energy of 1.6 – 3.1 eV or 157.4 – 299.1 kJ/mol.
Absorption of a particular component of
white light by a transparent material causes the Figure 29. Transmission curves for simple uncolored glass
appearance of color. If the material absorbs in a) P2 O5 glass; b) SiO2 glass; c) B2 O3 glass; d) HPO3 glass;
e) GeO2 glass
the red part of the spectrum, the color is blue;
absorption in the yellow region yields a brown The widest band gap among the glasses in
color. Thus, for it to have color, some light ab- Table 22 is shown by BeF2 . For oxide glasses,
sorption must occur in the glass. the absorption shifts to longer wavelength in
46 Glass
Table 21. Conversion values for wavelength, energies, and frequencies of light ∗

Wave- Wave- Energy Frequency,

number, length,
cm−1 nm eV kJ/mol kcal/mol 104 K 1014 Hz

400 25 000 0.050 4.824 1.143 576 0.1199

500 20 000 0.062 5.982 1.429 720 0.1499
1 000 10 000 0.124 11.964 2.859 1 439 0.2998
2 000 5 000 0.248 23.929 5.717 2 878 0.5997
3 000 3 333 0.372 35.893 8.576 4 317 0.8995
4 000 2 500 0.496 47.857 11.434 5 756 1.1990
5 000 2 000 0.620 59.822 14.293 7 195 1.4990
6 000 1 667 0.744 71.786 17.151 8 634 1.7990
7 000 1 429 0.868 83.750 20.010 10 073 2.0990
8 000 1 250 0.992 95.715 22.869 11 512 2.3990
9 000 1 111 1.116 107.679 25.727 12 951 2.6990
10 000 1 000 1.240 119.643 28.586 14 390 3.0000
11 000 909 1.364 131.608 31.444 15 829 3.2980
12 000 833 1.488 143.572 34.303 17 268 3.598
13 000 769 1.612 155.536 37.161 18 707 3.8980
14 000 714 1.736 167.501 40.020 20 146 4.1980
15 000 667 1.860 179.465 42.879 21 585 4.4970
16 000 625 1.984 191.429 45.737 23 024 4.797
17 000 588 2.108 203.394 48.596 24 463 5.097
18 000 556 2.232 215.358 51.454 25 902 5.397
19 000 526 2.356 227.322 54.313 27 341 5.697
20 000 500 2.480 239.287 57.171 28 780 5.997
25 000 400 3.100 299.108 71.464 35 975 7.496
30 000 333 3.720 358.930 85.757 43 170 8.995
35 000 286 4.340 418.752 100.050 50 365 10.494
40 000 250 4.960 478.574 114.343 57 560 10.871
45 000 222 5.580 538.395 128.636 64 755 13.492
50 000 200 6.120 590.498 141.084 71 022 14.798
55 000 182 6.820 658.039 157.222 79 145 16.495
60 000 167 7.440 717.860 171.514 86 340 17.990
65 000 154 8.060 777.682 185.870 93 535 19.489
70 000 143 8.680 837.504 200.100 100 730 20.988
75 000 133 9.299 897 229 214.370 107 914 22.485
80 000 125 9.919 957.051 228.663 115 109 23.984
85 000 118 10.539 1016.872 242.956 122 304 25.483
90 000 111 11.159 1076.694 257.248 129 499 26.982
95 000 105 11.779 1136.516 271.541 136 694 28.481
100 000 100 12.399 1196.337 285.834 143 889 29.980

∗Bold type indicates visible region of spectrum.

the increasing order P2 O5 , SiO2 , HPO3 , and
GeO2 . A further shift to longer wavelength oc-
curs when alkali-metal oxides are added to the
pure network-forming glasses. The degree of
shift can be correlated with cation field strength.
Addition of Li2 O to a network-forming glass
causes the smallest increase in wavelength; ad-
dition of Cs2 O, the largest.
Homogeneous glasses and crystals are col-
orless if the bandgap is sufficiently large. Thus,
Al2 O3 , SiO2 , and alkali-metal or alkaline-earth
oxides are colorless when pure. Coloring of
glass occurs because of the presence of impu-
rities, often transition metals, that absorb light
in the visible region. The reasons for this ab-
sorption are the transition-metal d orbitals. The
five d orbitals, which are degenerate in a free
transition-metal atom, are split into two groups
under the influence of the ligand electric field.
The split in energy between the two sets of d
orbitals is designated 10 Dq . Metal ions and lig-
and groups can be arranged in a spectrochem-
ical series: the metal ions according to the or-
der of increasing 10 Dq developed with given
ligand; the ligand groups according to the or-
der of increasing 10 Dq for any given metal ion.

The metal ions fall in the order Mn2+ < Ni2+ <
Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ <
Co3+ < Mn4+ < Mo3+ < Rh3+ < Ru3+ <
Pd4+ < Ir3+ < Re4+ < Pt4+ , and ligands in the
order I− < F− < H2 O < SCN− < NH3 < SO2− 3 of the visible region.
< NO− −
2 < CN . Tri- and higher valent metal
atoms tend to absorb in the visible region in ox-
ide glasses. Electronic transitions between lower
occupied and higher unoccupied states have an
energy value of 2 – 3 eV.
Figure 30. Calculated direct gap for the H6 Si2 O7 molecule
at a Si−O−Si angle of 180◦
The direct gap represents the difference in energy bet-
ween the highest occupied (HOMO) and lowest unoccupied
molecular orbital (LUMO).
The degree of splitting of the metal ion d
orbitals is affected by the coordination number
of the metal, oxidation state of the metal, sym-
metry of the coordination sphere, type of lig-
and, and nature of the metal ion. Splitting val-
ues (10 Dq ) for complexes of the first transition
series are 800 – 1333 nm for divalent ions and
Glass 47
400 – 714 nm for trivalent ions. Divalent ions,
therefore, absorb light outside the visible region
and tend to give only weak coloration arising
from absorption tails that extend into the red part
Table 23. Transition-metal colors in glasses
Metal Color
Titanium no color in low concentration; reduction of Ti(IV)
to Ti(III) in high concentration gives slightly
violet color; brown in phosphate glasses
Vanadium vanadium produces a variety of colors because of
its variable valence: green in silica glass;
colorless in alkali silicate glass; olive green in
phosphate glass; brown in borate glass
Chromium chromium(III) makes glasses green; oxidation
leads to chromium(VI) which is yellow
Manganese manganese(III) makes glasses violet;
manganese(II) gives a faint yellow
Iron iron(II) gives a green color to glasses molten in
neutral or slightly reducing atmosphere; iron(III)
gives yellow-brown glasses in combination with
sulfide (S2− )
Cobalt cobalt(III) gives intense blue color in silicate and
phosphate glasses; pink in lowalkali borate
glasses; green in glasses with very high alkali
content
Nickel nickel(III) gives olive green or brown color in
silicate glasses; higher alkali oxides give yellow;
lower content, a greenish brown; blue occurs in
some instances
Copper copper(II) gives blue in silicate glasses; reduction
to copper(I) leads to colorless glasses; green in
phosphate and borate glasses
Rare-earth cerium gives yellow; praseodymium, weak green;
metals neodymium, red to violet; erbium, pink
Producing a consistent, predictable color in
a glass is not trivial, because the same transi-
tion metal may give rise to a variety of col-
ors, depending on type of ligands and oxidation
state of the metal. This color variability for some
cobalt(III) complexes is shown below:
[Co(NH3 )6 ]3+ yellow
[Co(NH3 )5 H2 O]3+ pink
[Co(NH3 )5 Cl]2+ purple
[Co(NH3 )4 Cl2 ]+ ,
cis red violet
trans green
[Co(NH3 )4 (NO2 )2 ]+ ,
cis yellow brown
trans yellow red
Multinuclear Co complexes black
The most common transition-metal oxides
used in the glass industry and the expected colors
are listed in Table 23. Concentrations are typi-
cally 0.5 – 5 wt %. Varying oxidation conditions
48 Glass
can yield results spectacularly different from
those anticipated; for example, high-manganese
welding fluxes tend to be black to dark purple;
however, slightly reducing conditions make such
fluxes yellowish green. The colors in Table 23
should, therefore, be regarded only as guide-
lines.
Striking glasses are the second largest family
of colored glasses. Their color is caused by the
controlled nucleation and growth of a crystal-
like chalcogenide phase. These glasses form
the basis of commercial yellow-to-red sharp-
cut filters originally produced by Corning Glass
Works. The composition of these filter glasses is
given in Table 24.
Striking glasses are produced by casting and
fairly rapid cooling, which results in a colorless
glass. Rapid cooling causes a single burst of nu-
clei to form with similar dimensions, and reheat-
ing causes these nuclei to grow. Color develops
(strikes) after heat treatment of such glass bet-
ween 823 and 973 K. The absorption edge steep-
ens during striking and moves toward longer
wavelengths. By controlled reheating, isochemi-
cal glasses with different colors can be produced.
The most probable explanation for color gen-
eration in striking glass involves an electronic
transition from the occupied valence band to
the empty conduction band in semiconduct-
ing chalcogenide crystals in a silicate matrix.
The striking effect is specifically caused by the
variation in size of the gap as a function of
crystallite size, hence, the name quantum con-
finement for this effect. Typical striking glass
chromophores are CdS 2.42 eV (518 nm), CdSe
1.73 eV (717 nm), CdTe 1.44 eV (860 nm), and
ZnS 3.53 eV (340 nm) [125]. Of these, only CdS
and CdSe absorb in the visible region.
Striking glasses differ from those colored
by transition-metal ions mainly by the nearly
quantitative transmission of light from a spe-
cific wavelength to longer ones. The absorp-
tion and transmission regions are separated by a
sharp edge, making pure saturated colors possi-
ble. These glasses make excellent cutoff filters
for optical instruments, unlike filters based on
ionic colors with their characteristically broad
absorption bands.
5. Production of Glass
Glass-melting technology has passed through
six stages:
1) Glass manufacture in open pits ca. 3000 b.c.
until the invention of the blowpipe in ca.
250 b.c.
2) The mobile wood-fired melting pot furnace
used until about the 17th century by travel-
ling glass manufacturers.
3) The local pot furnace, fired by wood and coal
(1600 – 1850).
4) The gas-heated melting pot and tank furnaces
dating from 1860, followed by the electric
furnace of 1910.
5) Tank furnaces with special designs for ob-
taining better glass quality (since 1950).
6) All-oxygen-fired glass-melting furnaces
(since ca. 1985).
5.1. Raw Materials
Most glass requires heat to convert the raw ma-
terials such as minerals and synthetic inorganic
chemical components to a homogeneous melt at
fusion temperatures that turns to a rigid glass on
cooling. Raw materials are selected according
to purity, consistency, grain size, water content,
availability, pollution potential, ease of mixing
and melting, and cost. The most common ingre-
dients in glass production are listed in Table 25.
Today, the most important raw materials are
sand and recycled glass cullet. In Western Eu-
rope more than 7.5 × 106 t are recycled annually.
The primary contaminants are ceramics, organic
food residues, and paper. The metal contamina-
tions are almost completely removed from the
waste glass in modern post-consumer glass pu-
rification plants.
The primary contaminant in sands is Fe2 O3 ,
followed by minerals such as titania (ru-
tile), zircon (ZrSiO4 ), and chromia or iron
chromites. Acceptable limits for Fe2 O3 are
0.005 – 0.1 wt %, very much depending on the
glass product. Acid-washed varieties of sand
have the lowest iron concentrations. The price of
sand reflects the quality: varying between $ 15/t
for common glass to $ 800 – 1000/t for sand with
 Glass 49
Table 24. Composition of Corning sharp-cut filter glass [124] ∗

Component Composition, mol %

SiO2 73.5
Na2 O 5.8
B2 O3 10.5
Al2 O3 0.6
ZnO 8.9
CdO 0.3
Sb2 O3 0.2

Filter ∗∗ Cs 3-66 Cs 2-61 Cs 2-60 Cs 2-59 Cs 2-64

Se 0.06 0.11 0.11 0.13 0.19

S 0.09 0.07 0.05 0.06 0.04

∗ Base glass composition is determined by X-ray fluorescence, sulfur and selenium content by chemical analysis.
∗∗ The adsorption edges for the filters, as determined by photoluminescence, are as follows: Cs 3-66, 473; CS 2-61, 500; CS 2-60,
518; CS 2-59, 528; and CS 2-64, 546 nm.

Table 25. Raw materials used in glass production a

Raw material Chemical composition Glass-making oxide Oxide, wt %

Sand SiO2 b SiO2 99.8

Soda ash Na2 CO3 Na2 O 58.5
Trona Na2 CO3 · NaHCO3 · 2 H2 O Na2 O 41.9
Limestone CaCO3 CaO 56.0
Dolomite CaCO3 · MgCO3 CaO 30.5
MgO 21.5
Feldspar (K,Na)2 O · Al2 O3 · 6 SiO2 b SiO2 68.0
Al2 O3 18.5
(K,Na)2 O 12.8
Nepheline NaAlSiO4 b SiO2 60.6
Syenite Al2 O3 23.3
(K,Na)2 O 14.8
Petalite LiAlSi4 O10 Li2 O 4.9
Al2 O3 16.7
SiO2 78.4
Borax Na2 B4 O7 · 5 H2 O Na2 O 21.8
pentahydrate B2 O3 48.8
Boric acid H3 BO3 B2 O3 56.3
Colemanite Ca2 B6 O11 · 5 H2 O CaO 27.2
B 2 O3 51.0
Ulexite NaCaB5 O9 · 8 H2 O Na2 O 9.5
CaO 17.2
B 2 O3 53.7
Litharge PbO PbO 99.9
Anhydrous potash K2 CO3 K2 O 68.0
Potassium nitrate KNO3 K2 O 46.2
Fluorspar CaF2 CaO 69.9
Zinc oxide ZnO ZnO 100.0
Barium carbonate BaCO3 BaO 76.9
Strontium carbonate SrCO3 SrO 70.1
Sodium antimonate NaSbO3 Na2 O 16
Sb2 O3 75.6
Blast furnace slagsc x SiO2 · y CaO · z Al2 O3 + sulfide
a
Sulfates, chlorides, and fluorides are only partly retained in the melt. Sodium, potassium, lead, antimony, arsenic, and boron oxides
generally evaporate in small quantities from the melt; retention of these components in the glass is 90 – 99 %. Carbon dioxide and
nitrogen oxides are almost completely released from the batch blanket or glass melt. b Refractory components. c Composition is
source-dependent.
50 Glass
an iron content of only 15 – 20 mg/kg. For vit-
reous silica production, expensive high-quality
sands are used.
The main sources of calcium are lime-
stone and dolomite, which also supplies mag-
nesium. About 5 % of the total amount of
limestone quarried in the United States is con-
sumed in glass manufacture. Limestone contains
56 wt % CaO, and dolomite 30.0 wt % CaO and
21.5 wt % MgO. High-quality limestone con-
tains < 0.1 wt % Fe2 O3 and ca. 1 wt % silica and
alumina. A source of calcium carbonate for low-
iron glasses (ca. 0.02 wt % iron) is aragonite,
which is found in high purity in the Bahamas. A
drawback of this carbonate is the high content of
sulfates and organic material. Other raw materi-
als that are sources of calcium include coleman-
ite and fluorspar, often used in fiberglass pro-
duction, and iron blast furnace slags, used for
soda-lime glasses.
Trona, mined in Trona, Wyoming, is the pri-
mary source of soda in the United States. About
40 % of all soda ash produced in the United
States is consumed by the glass industry. Syn-
thetic soda produced from common salt (NaCl)
is used in Europe and contains small amounts
of residual sodium chloride (0.12 – 0.25 wt %).
Caustic soda solutions are sometimes used in
the wet batching process as a batch component
and as a dusting suppressant for subsequent han-
dling. When preparing agglomerated batch in
the form of pellets, caustic soda is used both as a
binder and as a sodium raw material. Worldwide
about 50 % of the soda production is consumed
by the glass industry.
Other raw materials for borosilicate glasses
include borax and boric acid. Colemanite and
ulexite are often preferred as sources of boron
on economic grounds. For glass compositions
with very low alkali concentrations such as E-
glass, colemanite or boric acid is used to avoid
an increased sodium content in the glass when
using other boron raw materials.
Feldspar and nepheline syenite are common
sources of alumina. In the container- and float-
glass industries, purified iron blast furnace slags
are used as an alumina-rich melting flux. These
slags also contain sulfides which decrease the
temperatures of primary fining (removal of bub-
bles, degassing). Litharge is used in the pro-
duction of lead silicate and lead-crystal glasses.
Powdered anthracite, corn starch, oil, raw pota-
toes, or sugar can be used as reducing agent. Typ-
ical oxidizing agents are nitrates such as potas-
sium or sodium nitrate, cerium(IV)oxide, and
sodium sulfates.
Most commercial glass compositions contain
small amounts of other constituents which, in
general, do not significantly affect the physi-
cal properties of the glass. Fining agents are
added in small amounts to eliminate gas bubbles
formed during melting. Common fining agents
are sulfates, halides (e.g., NaCl), CeO2 , MnO2 ,
As2 O5 , and Sb2 O5 . These agents are thought to
release oxygen, sulfur dioxide, or other gases,
increasing the size of the gas bubbles and there-
fore their buoyancy in the melt. The melts dis-
solve gases such as carbon dioxide, nitrogen, wa-
ter vapor, oxygen, and argon that originate from
decomposition of the raw material or from the
furnace atmosphere. Most of these gases can be
removed from the melt by the growing and as-
cending bubbles during the fining process. Some
fining agents, like sodium sulfate, cerium(IV)
oxides, antimonates or arsenates also oxidize the
glass melt and reduce the iron(II) concentration
by oxidation reactions. Nitrates are often used
to oxidize batch components such as As2 O3 (to
As2 O5 ) and Sb2 O3 (to Sb2 O5 ) in order to make
these components effective for primary fining.
Refractory batch components are materials
with a high melting point which exceeds the
maximum temperatures in the melting tank.
These components do not simply melt but dis-
solve in the primary melts of the other raw ma-
terials. Alumina and sand grains, for example,
react with and dissolve in sodium-, potassium-,
and boron-rich melt phases. The dissolution
rates depend on temperature, composition of the
primary melts, and the size of the refractory
batch grains.
Besides purity, the grain-size distribution of
the refractory batch materials is an important
factor in successful melting. Too coarse a frac-
tion results in incomplete dissolution of the sand
or alumina raw material in the primary melts,
with attendant stones and knots in the glass; too
fine a fraction results in dusting during handling
and too rapid melting, which leads to very fine
gaseous inclusions (seeds). The latter may also
result in the formation of an insulating alumina
or silica-rich scum on top of the glass melt. This
scum, due to flotation of very fine silica or alu-
mina grains and subsequent sintering on top of
 Glass 51

the melt, can decrease the heat transfer into the producing fine-grained sand. Fiberglass manu-
melt and slow the rate of melting. In some critical facturers, on the other hand, use sand with di-
cases, the scum may form silica- or alumina-rich mensions < 74 µm (200 mesh). The conversion
glass defects or cords. between mesh size, micrometers, and inches is
given in Table 26.
Table 26. Conversion table for micrometers, mesh, and inches
Batches with raw materials having different
Micrometer Inch Mesh∗ grain size distributions are sensitive to batch seg-
regation. Most glass melting batches show this
4760 0.185 4
3360 0.131 6 behavior during dry transport especially during
2380 0.093 8 vibration and free fall. Therefore, water or some-
1680 0.065 12 times light oil is added to prevent demixing dur-
1190 0.046 16
840 0.0328 20
ing transport and charging of the batch feed into
590 0.0232 30 the furnace. Wetting of the batch also reduces
420 0.0164 40 the entrainment of fine batch components in the
297 0.0116 50 combustion gases in the furnace. This entrain-
250 0.0097 60
210 0.0082 70
ment or batch carryover can lead to batch losses
177 0.0069 80 but also to fouling of the flue-gas channels and
149 0.0058 100 equipment downstream of the flue-gas ducts.
105 0.0041 140
74 0.0029 200
62 0.0024 230
53 0.0021 270
5.1.1. Chemical Impurities and Decoloration
44 0.0017 325
37 0.0015 400 Pure minerals do not occur in nature. Contami-
20 0.0008 625 nants such as transition metals, sulfates, halides,
10 0.0004 1250 or organic matter are always present. Natural or
5 0.0002 2500
upgraded ores are used, depending on the glass
∗ Tyler Standard Screens; note that five other standards are specifications. The most common impurity is
commonly employed: (1) British Standard Test Sieves, (2)
Institute of Mining and Metallurgy, (3) the German DIN, (4) the
iron, whose presence is usually undesirable for
French AFNOR, and (5) the U.S. Standard Sieve Series. clear and flint glasses. Upper limits for this ele-
ment in some glass products are listed below in
Nework modifiers increase the melting rate percent by weight:
and generally decrease the viscosity of the melt. Optical waveguides 10−6
Their effect is to start the dissolution of refrac- UV transparent Schott glass 0.004
tory materials, and to decrease the viscosity and 8337
Lead glass 0.018
surface tension of the melt. They commonly Ophthalmic glass 0.020
have a low melting point and high vapor pres- Container flint glass 0.035
sure. A low surface tension of the melt improves Container green glass 0.25 – 0.35
Container amber glass 0.30
the wetting of the surface of the refractory batch Flat glass (clear) 0.07 – 0.1
grains by the aggressive primary melts. Some ef- Tinted flat glass ≤ 1.6
ficient melting fluxes apart from network mod- Tableware (clear) 0.02
ifiers are sodium sulfate, sodium chloride, and
calcium fluoride (fluorspar), which have a low Other undesirable impurities include primar-
surface tension, cullet which needs no fusion en- ily the colored oxides of transition metals (e.g.,
ergy, and slags containing sulfides and alumina nickel, vanadium, copper, manganese, chromi-
in an easy-to-melt form. um, cerium, and cobalt). In addition to coloring
Melting considerations tend to favor grain agents, excess sulfate may cause sulfate gall for-
sizes of refractory batch components that are one mation on top of the melt and sodium sulfate
to two screen sizes finer than those of commer- inclusion in the glass. Too much sulfate may
cially available fluxes. Container glass manu- also lead to precipitation of SO2 seeds in the
facturers generally use sand between 100 and glass. Sulfate-containing melts prepared under
600 µm (140 – 30 mesh) as the best compromise relatively strong reducing conditions may form
between melting efficiency and the high cost of SO2 bubbles which, if not completely removed,
52 Glass
generate low-pressure blisters with sulfur and
sulfate deposits in the final product [135]. The
presence of chloride impurities in raw mate-
rials leads to chloride-containing melts, which
may attack the forming molds. Ammonia, coke,
sulfides, and organic materials affect the oxy-
gen fugacity (equilibrium pressure of dissolved
oxygen gas) of the melt, with attendant reduc-
tion of transition metals and subsequent color
changes, e.g., reduction of Ti4+ (colorless) to
Ti3+ (blue) or increased concentration of Fe2+
due to reduction of Fe3+ , or formation of S2− ,
which forms an amber chromophor in combina-
tion with Fe3+ .
Impurities are not always undesirable. Small
amounts of iron are sometimes necessary to de-
velop a certain glass color. During melting, these
impurities often influence heat radiation into
the glass, and during forming, they affect the
heat loss to the mold or environment. Iron(II)
sulfide (FeS) and iron pyrites (FeS2 ) produce
amber-colored glass used in the container indus-
try. The residual Fe3+ forms an iron(III) sulfide
oxide complex with S2− giving the glass the am-
ber color. Green container glasses use sodium
dichromate or iron chromates. Green and am-
ber container glasses protect beverages, pharma-
ceuticals, and foods against UV radiation. Sele-
nium, with iron and cobalt, yields a bronze color.
In small quantites, selenium, added as elemental
selenium, selenite, or selenate, often in combi-
nation with cobalt oxides, decolorizes glasses
containing iron(II). Selenium plus cobalt ox-
ide give the glass the complementary color of
the iron(III) coloring. Cerium dioxide is used
to increase UV absorption in optical or color-
less soda-lime glass and protects against X-ray
browning.
Mass-produced glasses tend to use cheap
raw materials with fairly high concentrations of
iron. Especially iron(II) gives the glass a green
color. Physical or chemical decoloration of such
glasses is therefore important. In chemical de-
coloration, the iron is oxidized to its weakly
colored trivalent state by increasing the oxygen
fugacity of the melt, usually by adding oxygen-
producing compounds such as As2 O5 (or arsen-
ates), Sb2 O5 (or antimonates), KNO3 , NaNO3 ,
Na2 SO4 , and CeO2 . Chemical decoloration is
effective if the iron concentration does not ex-
ceed 0.02 – 0.1 wt %. Physical decoloration is
used when the melt contains a higher concentra-
tion. Here, the addition of other coloring agents
compensates for the yellow-green color of the
glass. Common compensating agents are sele-
nium and manganese dioxides with a purple to
pink coloration, and the oxides of cobalt, nickel,
or neodymium. A side effect of physical decol-
oration is a reduction in total light transmission.
The redox state, determined by the oxygen
fugacity of the melt, determines the color of the
glass, because dissolved oxygen has a strong in-
fluence on the redox state of polyvalent ions such
as iron, chromium, and sulfur in the melt. The
color of the glass very much depends on the ox-
idation state of these ions.
5.1.2. Waste Glass (Cullet)
Waste glass, known as cullet, is an almost univer-
sal addition to the batch melted in glass furnaces
[136]. In Western Europe some countries, in-
cluding Germany, the Netherlands, and Switzer-
land, recycle more than 80 % of the container
glass brought onto the market. Recycled cullet
saves the resources of other raw materials, re-
quires up to 25 – 30 % less energy to melt than
an isochemical batch of raw materials, and, pro-
vided it is not too fine, reduces dust during batch-
ing and carryover of dust from the batch blanket
in the furnace. Optimized furnaces using large
cullet ratios in the batches have lower specific
nitrogen oxide and carbon dioxide emissions.
Typical amounts of cullet used in different
glasses are listed below, in weight per cent:
Container glass 25 – 95
Flat glass 20 – 35
Light-bulb glass 40 – 70
Tableware 25 – 50
TV glass 20 – 45
Insulation glass wool 40 – 45
Commercial glass 50 – 70
In container and insulation-wool glass fur-
naces, large quantities of external cullet can be
recycled. Flat glass, TV glass, tableware, and
lighting-glass furnaces use their own cullet or
cullet from well-identified sources.
Generally, about 10 – 30 % of the cullet
comes from crushed recycled glass produced in
the plant. Iron contamination introduced by the
crushing process is removed magnetically. Cul-
let of unknown origin, often collected from bins

specially installed for household glass waste dis-
posal, commonly contains impurities that may
be incompatible with the desired quality of the
manufactured article, giving unwanted color,
stones, crystals, metallic inclusions, cords, or
gas bubbles. Metallic impurities in the cullet
form liquid metal melts that can react with the
refractory and may also cause holes in the bot-
tom of the melting unit (downward drilling).
Recycled bottles constitute up to 80 % of the
batch used in the container glass industry in
some Western European and Asian/Pacific Rim
countries. This amount is expected to increase
substantially in other parts of the world with
the increasing introduction of recycling laws in
the United States, Eastern Europe, Canada, and
probably South America.
The insulation glass wool industry uses flat
glass cullet as one of the main raw materials.
Another waste material added as a raw mate-
rial to glass melting batches is filter dust sepa-
rated from the glass furnace flue gases by elec-
trostatic precipitators or baghouse filters. This
filter dust often contains sulfates, sodium, and
lime, and it can replace part of the sodium sul-
fate used as a fining agent in the batch.
5.1.3. Preparation of Raw Materials
Accuracy and precision in weighing the vari-
ous batch constituents are important, because of
the required consistency in glass composition.
Thorough mixing of ingredients and prevention
of subsequent segregation is essential to obtain
a homogeneous glass melt. Batch handling sys-
tems vary widely throughout the industry, from
manual for small production sites to fully auto-
matic (→ Solids Handling). Some glass facto-
ries purchase their batches in granulated form
(granule size 8 – 20 mm). In large-volume pro-
duction, each batch material is stored in its own
bin, and the correct computer-controlled amount
is weighed from the bin onto a conveyor belt that
feeds directly into an intensive mixer.
The efficiency of the melting operation and
the uniformity and quality of the glass are often
determined by the conveyance of the raw mate-
rials and the quality of mixing. Mixing of small
amounts of specific raw materials, such as fin-
ing agents, coloring/decoloring compounds or
cokes, to the bulk of the batch is carried out just
Glass 53
before delivery of the batch to the furnace to
prevent segregation. Different types of batches
use different mixers. For instance, high-silica
glasses such as soda-lime, borosilicate, and alu-
minosilicate are mixed in pan-type mixers with
vertical stirrers. The batch is first dry-blended,
followed by addition of a small amount of liq-
uid (up to 3 – 4 wt % water or oil) for wet blend-
ing. The whole operation takes 3 – 8 min; longer
treatment may result in segregation. A typical
batch size may be a few hundred up to 4000 kg
of material.
Many speciality glasses, especially those
with high-density components such as PbO,
were once mixed either in muller-type mixers
or in horizontally rotating drums, but these mix-
ers lead to segregation due to free-fall move-
ment. High-intensity mixers with vertical stir-
rers are now commonly used. Wet mixing and
batch agglomeration-pelletizing, briquetting or
compaction are becoming popular for several
reasons, one of which is the avoidance of dust
formation, especially during preparation and
transport of raw materials containing hazardous
components like lead and arsenic-containing
batches. Other reasons are prevention of carry-
over in the furnace, absence of segregation, and
hence better homogeneity, which improves glass
quality. Radiative heat penetrates pelletized ma-
terial faster than batch blankets containing nor-
mal raw materials, the single grains in the pellets
are bound to the other grains, increasing reactiv-
ity during the fusion processes. The use of pellets
lowers the energy demand of the glass furnace or
allows higher melting loads in a glass furnace.
Cullet is generally added to the mixed batch
just before mixer discharge. Sometimes the cul-
let or the cullet plus normal batch is preheated by
raw material preheaters using the flue gas heat
contents.
5.2. Melting Units
Most glass is produced by continuous melting
processes. Only glasses with special character-
istics are manufactured in batch-type processes,
which allow greater compositional flexibility.
Small production sites manufacturing lead crys-
tal or art glasses often use batch-type processes
such as pot furnaces. The function of glass fur-
naces is the conversion of raw materials into a
54 Glass
homogeneous melt, free of inclusions. In the fur-
nace chemical reactions between batch compo-
nents leading to fusion and melting takes place.
Complete melting is necessary to produce a glass
without batch stones. The dissolved gases and
gas bubbles should be removed from the melt
and the melt homogenized, because small differ-
ence in chemical composition cause variations
in refractive index or lead to thermal stresses in
the final products.
5.2.1. Flat Glass and Container Glass Tanks
Volume production of technical glass is carried
out exclusively in rectangular, relatively shallow
glass tanks, capable of holding up to 1200 t of
melt. The tank functions as a rectangular melting
crucible, directly heated from the top by flames
or in the melt by electrodes. Convection in the
melt mixes the heated surface of the glass melt
with the rest of the melt.
The tank is covered at the top by a vault (arch)
of silica bricks, known as the cupola or crown,
supported by sidewalls which are constructed
from different materials: refractories for high
temperatures at the inside and insulation bricks
or mats at the outside. The total thickness can
be 600 – 800 mm. The crowns are constructed
mainly from silica or mullite (Al6 Si2 O13 ), but
in some cases fusion-cast refractories are used.
For the inner layers of the sidewalls, fused-cast
alumina – zirconia – silica (AZS) refractory ma-
terials and, for some furnaces, chromium oxide
refractories are used. The outer layers provide
thermal insulation to the furnace.
The melting tank is divided into two sections
by a permanent bridge wall or by floating refrac-
tory baffles. The larger section into which the fill
(i.e., batch plus cullet) is charged by means of
the batch house – a small extension (called dog-
house) of the furnace in the backwall – is called
the melting end. The batch plus cullet floats on
top of the melt as a blanket or as batch islands.
The batch blanket is continuously fed by new
raw materials and extends several meters into
the melting end. The other separated section of
the tank, in which the melt starts to cool and to
condition toward its uniform working viscosity,
is called the working or refining end (refiner).
Partitioning of the tank into two parts allows
continuous production of glass. The working
and melting ends are connected by a neck (large
float glass furnaces) or a throat. Most container-
glass and tableware furnaces are designed with a
throat, a covered channel through which the melt
flows from the melting end into the bottom sec-
tion of the working end. In furnaces with a neck,
the glass melt flows into the working end without
a contact with refractories at the surface. Some
furnaces with a direct connection between melt-
ing end and refiner use a skimmer to prevent the
flow of surface glass that differs from the bulk
glass or to prevent the surface scum to flow into
the refiner tank.
The melting tank depth is generally 50 –
150 cm, depending on the transmission of ther-
mal radiation from the flames in the combus-
tion chamber on top of the tank to the molten
glass. The melting tank design depends also on
the glass composition, melting rate, type of fuel
and oxidant (air or oxygen), and production rate.
Tank parts that come in contact with the melt
are usually made of highly refractory fusion-
cast AZS or chromium oxide blocks. A typical
Siemens-type side port fired continuous tank is
shown in Figure 31.
Figure 31. Fossil fuel fired Siemens-type regenerative fur-
nace for container glass production
a) Doghouse; b) Fuel-injection lance; c) Melting end;
d) Burner block; e) Throat; f) Working end; g) Regenerator;
h) Checkerwork (an open structure of bricks); i) Air/fuel re-
versal mechanism; j) Chimney damper; k) Air inlet; l) Waste
gas exit.
The conventional side-port regenerative fur-
nace shown in Figure 31 is equipped with two
regenerator sections on each side. Each regener-
ator is connected to the furnace by four to seven
ports. During a period of 20 – 35 min ambient
air is conducted to the left-hand regenerator for
preheating. The hot air (1100 – 1300 ◦ C) flows
through the ports into the combustion chamber

of the furnace. In the combustion chamber air is
mixed slowly with fuel oil or natural gas injected
by one to three lances per port. The mixture pro-
duces a flame with a maximum temperature of
about 2000 ◦ C in this furnace type.
Figure 32. Top-view schematics of fossil-fuel-fired tank fur-
naces
A) Cross-fired regenerative furnace; B) End-port furnace
with regenerators at the backwall; C) Recuperative furnace
with a flue gas/air heat exchanger; D) All-oxygen-fired fur-
nace (without preheating of oxygen)
After 8 – 12 s, the gases exit the furnace and
heat the opposite regenerator chambers. After
Glass 55
20 – 35 min, the air and fuel flows are switched,
and the preheated regenerator on the right-hand
side is used to heat the combustion air. Thus air,
flames, and flue gas flows are reversed every 20 –
35 min. By this method about 45 – 50 % of the
energy content of the fuel is transferred to the
melt for heating and fusion reactions. In direct-
fired glass melters without air preheating, the
combustion air energy efficiency is much lower.
Schematics of other furnaces in top view are
shown in Figure 32.
In the recuperative furnace the flue gases pre-
heat the air in heat exchanger type recuperators;
the flue gases are cooled from about 1250 – 1300
to 800 – 900 ◦ C, and air is preheated to about
750 ◦ C. The furnace is often constructed as a unit
tank (simple rectangular tank shape) furnace.
Similar furnaces but without recuperators and
special burner designs are used for all-oxygen-
fired tanks, which have been replacing some of
the larger air-fired regenerative and recuperative
furnaces since 1991.
Some glass melting tanks are provided with
electrodes to boost the energy supply to the
melt. Forced bubbling improves mixing and heat
transfer into the melt. Short cut melt flow along
the bottom of the tank prior to its exiting through
the throat or neck can be suppressed by a weir or
dam, the refractory material of which must with-
stand high temperatures and glass-melt veloc-
ities. Molybdenum-reinforced AZS weirs and
chromium oxide refractory walls are sometimes
used.
Some tanks are equipped with a section called
a deep refiner, which is much deeper than the
first part of the melter. The deep refiner allows
the bubbles to be more efficiently removed from
the melt. The deep refiner is connected to the
working end by a throat. In most cases the first
section of the melting tank and the deep refiner
are separated by a flow barrier. Special furnace
designs are often patented by specialized glass
furnace construction companies.
Optimum tank design is still being stud-
ied. Simulation models are based on three-
dimensional finite-element numerical proce-
dures (Computational Fluid Dynamic codes).
Numerical models are based on conservation of
mass, energy, momentum, and electric charge
or potential. The models predict heat transfer,
melting rates, temperatures and glass melt flow
patterns in the tank. Some models also include
56 Glass
the combustion process and heat transfer in the
combustion chamber. The results of such cal-
culations for the temperature distribution in a
rectangular glass tank with a combustion cham-
ber on top are shown in Figure 33. A review of
the status of computational techniques applied to
tank design and a comparison of different mod-
els is given in [137].
Important in glass furnace design is a melting
tank with extra means to improve heat transfer
and which shows a good melting, fining, and ho-
mogenization performance. Short-cut flow pat-
terns along the relatively cold bottom should be
avoided, and separation of a first loop and a sec-
ond convection loop in the melting tank may
be essential for obtaining a sufficiently degassed
and homogeneous glass melt. Numerical glass-
tank models can be used to find the optimum fur-
nace design or process conditions with respect
to stability, glass quality, energy efficiency, and
emissions [138].
Producers of flat glass use the largest tanks
with surface areas of 400 – 800 m2 . The fill is
distributed evenly over the full width of the
tank by auger screws in barrels through multiple
openings in the back wall, by pusher bars, or by
vibratory plates. The last two methods often act
in concert to form a blanket fill across the rear
of the melting-end surface. A refractory exten-
sion of the melting end, called the doghouse, is
frequently used to fuse the fill before it moves
into the melting end itself. Container-glass tanks
are smaller, with melting end surface areas up to
140 m2 , and often no blanket fill is used. Most
container-glass furnaces are constructed as end-
port-fired regenerative furnaces, and one or two
screw feeders in small extensions of the side-
wall(s) supply the batch to the top of the melt.
The batch generally floats on top of the melt
as small islands that together form a caterpillar-
shaped batch line.
In sufficiently wide cross-fired tanks, cross-
firing ports in the sidewalls are connected to re-
generator chambers. In smaller tanks, the ports
are usually in the backwall; these types of fur-
naces are called end-port-fired or U-flame fur-
naces. Regenerator chambers, which operate in
pairs, are used to economize on fossil fuel by ex-
tracting heat from the flue gas before it is emit-
ted through the stack. In U-flame furnaces, the
strongly elongated flames make a U-turn, and
the exhaust port and air inlet port are both in the
backwall.
Temperatures up to 1400 – 1600 ◦ C, may be
required to melt the fill and to remove the gas
bubbles from the melt, depending on the type
and quality requirements of the glass. The tem-
perature limit of a tank is determined by the qual-
ity of the superstructure material and the melt-
line attack (i.e., increased wear of the refractory
at the contact refractory – melt – furnace atmo-
sphere). The weakest points that determine the
lifetime of a glass-melting furnace are the throat,
the refractories at the melt-line positions, and
sometimes the crown and the regenerators. Car-
bon dioxide from carbonate-containing batch in-
gredients together with water and air trapped
in the interstices of the fill, produces an ini-
tially foamy melt. Temperature profiles along
the length of the tank are controlled to ensure
that all batch material is dissolved in the fresh
melt and that fining agents remove gaseous in-
clusions before the glass passes into the refining
end of the tank. In some furnaces the surface
of the melt (containing scum or foam) in the
melting end is skimmed off by floating baffles.
In most tableware, container-glass, and lighting-
glass furnaces, the melt exits the tank or refining
end through a throat in the solid bridge wall.
The principal working characteristics of glass
melting tanks are melt efficiency and energy
consumption, which depend on the glass type.
For float glass a specific load of 1.5 t m−2 d−1
of melt and 6500 kJ/kg of glass melt are typical;
for container glass 2.5 – 3.5 t m−2 d−1 of glass
can be melted with a specific energy consump-
tion, depending on cullet ratio in the batch, of
3600 – 5.000 kJ/kg. Higher energy requirements
(8000 kJ/kg) and lower specific melting loads
(< 1.5 t m−2 d−1 ) have to be accepted for TV
panel glass because of the required high quality.
Enlarging and locally deepening the tank in-
creases the allowable throughput, especially for
colorless glasses. Additional heating by elec-
trodes is required for deeper tanks. Applying
an a.c. voltage between molybdenum or tin ox-
ide electrodes in the melt generates heat in pro-
portion to the square of the electric current and
the glass melt resistance. Bubbling air or steam
helps to achieve an even bath temperature and
the extra mixing provides a better homogeneity.
The life span of a tank depends on the quality
of the refractory bricks. Modern container-glass

Figure 33. Temperature contours calculated for a end-port-fired regenerative container glass furnace. The surface temperatures
and cross-section temperatures along the length axis are presented. Red: > 1450 ◦ C, blue: < 1350 ◦ C. The initial part of the
flames calculated by the simulation model is also shown.
tanks are designed to be used for six to eight
years before rebuilding is necessary. Float-glass
furnaces producing the melt to be shaped as flat
glass reach lifetimes up to 13 years before re-
building.
5.2.2. Unit Melters
Recuperatively fired unit melters are used for
continuous production of high-quality optical or
ophthalmic glasses, soda-lime glasses for drink-
ing bottles, and glass fibers or opal glasses.
Often, typical tank dimensions are small: 2 –
5 m wide, 10 – 12 m long, containing 4 – 100 t of
melt. Larger melters are generally designed as
regeneratively fired furnaces or as oxy-fuel fired
melters, but recuperatively fired unit melters
with production rates of up to 150 t/d exist.
Some unit melters are directly fired without
any air preheating, but they have a very poor en-
ergy efficiency and very low melting loads. To-
day, directly fired furnaces are only used in de-
veloping countries. In recuperatively fired and
directly fired unit melters the combustion air
and fuel are premixed in small burners and the
flames cover the glass-melt surface. Firing tem-
peratures of at least 1600 ◦ C can be reached by
positioning the burners opposite each another
or in staggered arrangement. The specific melt-
ing loads barely exceed values of 1.5 t m−2 d−1 .
Low heating efficiency and higher operating
costs offset the lower capital investments of unit
Glass 57
melters compared with container- and flat-glass
tanks. Unit melters are economical only in pro-
cesses that require fairly small quantities of glass
or rapid changes in glass composition.
5.2.3. All-Oxygen-Fired Melters
Improvements in the technology for separating
oxygen from air by cryogenic or selective gas ab-
sorption techniques in the 1980s and 1990s and
strict emission limits for nitrogen oxides justi-
fied the use of oxygen instead of air for the com-
bustion of fossil fuels in glass furnaces in nu-
merous glass-melting operations in the United
States, Central America, South America, Korea,
Japan, and Europe. Instead of preheated air, pure
or almost pure oxygen is used as oxidant for fuel
combustion. The furnace atmosphere is amost
free of nitrogen, whereas air-fired furnaces have
nitrogen concentrations of about 65 vol %. The
volume flows of flue gases are only 15 – 25 % of
those of similar air-fired furnaces. These much
lower volume flows of hot flue gases result in
much smaller energy losses than in air-fired fur-
naces. Due to the low volume flows and the risks
of preheating oxygen, the flue gas heat is not
recovered. Only in a few cases the flue gases are
used to preheat part of the batch.
Most oxygen-fired melters are constructed
similarly to unit melters. Generally, three to five
burner blocks are installed in each sidewall. Typ-
ical oxygen burners have separate nozzles for
58 Glass
oxygen and for atomized fuel oil or natural gas.
The luminescence of the flames can be improved
by delayed oxygen – fuel mixing, which creates
soot particles. The furnace atmosphere contains
high concentrations of volatilized components
from the batch blanket and glass-melt surface.
Precautions must be taken to protect the com-
bustion chamber refractories from the aggres-
sive vapors.
Oxygen-fired furnaces show low energy con-
sumption, although the energy requirement for
the oxygen production also must be taken into
account. The nitrogen oxide emissions and par-
ticulate emissions are generally lower com-
pared to air-fired furnaces [139]. Specific melt-
ing loads of up to 2.5 t m−2 d−1 for oxygen-fired
container-glass furnaces are feasible.
5.2.4. Electrical Melting Units
In some countries, all-electric melting in glass
furnaces has become a leading objective for eco-
nomic and environmental reasons. The method
is based on the electrical conductivity (Joule
heating) of a melt. Electrical conductivity in-
creases as a function of temperature. The con-
ductivity is caused by the presence of mobile al-
kali and alkaline earth metal oxides in the glass.
Low-frequency (50 – 60 Hz) alternating current
is used to minimize energy dissipation resulting
from the activation energy required for electrical
conduction.
The all-electric vertical melter is charged
from the top, and the fresh batch layer covers
the complete melt. Because of the relatively cold
batch on top, these melters are also called cold-
top electric melters. The crown or roof of the
furnace is also relatively cold. Most vapors from
the hot melt are entrapped in the batch layer, un-
less part of the melt is not covered, and therefore
emissions of these melters are very low com-
pared to fossil-fuel-fired melters with uncovered
glass melts. For example, in an air-fired fur-
nace up to 40 % of the fluorine evaporates and
is lost, compared with only 2 % in an electric
melter. Especially for glass or batch composi-
tions containing volatile or environmentally haz-
ardous volatile components an all-electric cold-
top furnace offers an environmentally sound al-
ternative. Production is usually limited to small
charges of 4 t/d, although larger units with 120-
t/d capacity also exist.
Molybdenum, tin oxide, sometimes graphite
(under reducing conditions), or platinum elec-
trodes extend from the bottom or well into the
melt. A cold-top furnace is shown in Figure 34.
Figure 34. Cold-top electric glass melting tank
a) Blanket of batch; b) Melt; c) Molybdenum liner (not al-
ways necessary); d) Molybdenum pipe or refractory canal;
e) Riser; f) Forehearth/working end; g) Electrodes
Electrodes can extend through the bottom as
vertical rods, horizontally through the sidewalls,
or can dip into the melt through the batch blan-
ket. During the heating phase, burners are used
to bring the cullet or batch in the furnace up to
temperatures at which the electrical resistivity of
the melt becomes low enough to conduct elec-
tric current. The burners are then removed, and
the electrodes provide all the energy required for
melting, fining, and homogenization. Controlled
convection of the melt is important to obtain a
homogeneous melt and to avoid short-cut flows.
An additional advantage of electric heating
is the control of glass composition, especially
when using volatile components, which is par-
ticularly useful in the production of certain op-
tical glasses. Controlling the reaction between
the batch blanket and molten glass in the reac-
tion zone is of special importance. First a melt of
the low-melting components is formed, and the
refractory batch components dissolve in these
primary melts. Just after melting, in the hottest
zones, the fining process occurs. Bubbles are
released from the melt and escape through the
pores in the batch blanket. In cold-top electric
melters gases released from the melt must find
a way through the fill. Because of this and the

possibility of fresh cold dense melt flowing di-
rectly to the bottom of the tank, the fining pro-
cess can sometimes become critical and unsta-
ble. The molten glass flows from the melting end
through a throat or canal into a riser and into the
working end.
Production of optical glass represents the
epitome of criteria for glass homogeneity and
freedom from flaws. Platinum crucibles are used
to produce blister-free glass at a temperature up
to 1550 – 1600 ◦ C. The platinum-covered vaults
of the melting section are usually made of zircon
or silica bricks, depending on the type of glass
being produced. Older burner systems have been
replaced by environmentally safer platinum, tin
oxide, or molybdenum electrodes.
Electrical melting has some disadvantages,
including the higher energy cost, which is only
partly offset by the lower amount of energy re-
quired (2500 – 4000 kJ per kilogram of glass),
and the more rapid decrepitation of the refrac-
tory material compared to conventional units.
Hence, the working life of a typical cold-top
electric melter is only about 50 % of that of
the lifetime of regeneratively fired glass melt-
ing tank furnaces. The advantages, such as small
units, low capital investment, flexibility in types
of batch materials, small vaporization loss of
expensive or environmentally hazardous com-
ponents, no nitrogen oxide emissions in case of
raw material batches without nitrates, and par-
ticularly environmental compatibility, make re-
sistance heating by electrodes sometimes an at-
tractive proposition.
5.2.5. New Melter Designs
An overview of alternative melting technolo-
gies is given in [140]. Most alternative melt-
ing methods have separate sections for melting,
degassing/fining, and conditioning or homoge-
nization. The melting zone can even be divided
into a batch preheating area, a primary melting
stage, and a final melting and firing stage.
Some new concepts use subatmospheric-
pressure fining to enhance bubble and gas re-
moval from glass melts, and some melters use
centrifugal forces to separate the gaseous inclu-
sions from the molten glass.
A combination of batch preheating, firing at
low temperatures to reduce NOx formation, and
Glass 59
separate zones for melting, fining, and refining
and conditioning is presented by the LoNOx
Melter developed in the mid-1980s in Germany
(Fig. 35) [141].
Figure 35. Design of the Sorg LoNOx melter for container-
glass melting
5.2.6. Pot Furnaces and Day Tanks
Pot furnaces are scaled-up research furnaces.
The name derives from the use of monolithic
high-quality clay pots to contain the molten
glass. Generally, the freshly prepared pots are
tempered slowly at 900 ◦ C by electric heating,
prefired at 1200 ◦ C, and fired to obtain a dense
low-porous material at about 1400 ◦ C in the pot
furnace itself. Most pots are made of aluminum
silicate materials. Open pots containing 150 –
1000 kg of melt are still used in Europe to manu-
facture colored and optical glasses as well as
crystal glass. Typical areas in Europe using pot
furnaces for art glass or crystal glass are the
Venice area (Murano island) in Italy, the South of
Sweden, the Czech Republic, the Bavarian forest
in Germany, and some areas in Portugal, France,
and in the vicinity of Birmingham in the United
Kingdom. Closed pots surrounded by refractory
brick walls were the preferred setup in the United
States. The largest pot furnaces contain eight to
ten pots, each with a diameter of about 0.7 – 1 m.
Today, pot furnaces are hardly used in the United
States because of their low energy efficiency and
operational fluctuations, which can lead to vari-
ations in glass quality. Only for small production
sites manufacturing handmade glass objects, pot
furnaces are still applied.
The type of batch and glass specification de-
termine the manner in which the pots are used.
A typical melt cycle for crystal glass production
in a pot furnace takes about 17 h and entails the
60 Glass
following: 6 h to melt the first fill, 2.5 h melting
after addition of a second batch, 7 h melting and
fining after adding a third batch at the highest
temperature level close to 1350 – 1400 ◦ C, and
finally a lower temperature stage for 1.5 h to
refine and condition the melt. The working tem-
perature at which the glass melt is collected from
the pot for forming processes depends on the
glass composition and is in the range of 1100 –
1200 ◦ C.
Production of specialty, high-value products
(e.g., specially colored glass) or enamel glass
frits is often carried out in day tanks. These
tanks, usually built from refractory bricks, are
typically heated rapidly by one to three pairs of
oil or gas burners and produce 1 – 5 t/d of glass.
The glass melt depth is only 10 – 20 cm. These
day tank furnaces are particularly well suited
for the manufacture of soft (i.e., low-viscosity)
glass, such as crystal or soda-lime glass, which
requires special production techniques. They are
not as well suited for the manufacture of low
thermal expansion borosilicate glasses because
of the high boron loss during rapid heating. Such
glasses can be produced if less rapid heating is
used, with an increase in the average melting and
fining time to 48 h. Even then, silica-rich stones,
crystals, or cords, resulting from loss of sodium
or boron at the surface of the melt, may still be
found in the glass.
5.3. Melting, Fining, and
Homogenization
The three steps involved in the production of
a glass melt are melting, fining, and homoge-
nization. The cold batch is charged to the tank
or pot and melted at 1200 – 1650 ◦ C, depending
on the type of glass. Decarbonation and dehy-
dration are the first chemical processes to take
place in the batch, followed by partial melting
and sintering as the eutectic temperature of some
batch components is reached. Several new crys-
talline phases can be formed, and depending
on the temperature ranges, can melt or dissolve
in eutectic melts. Some of the sulfate, almost
all carbonate, and water are removed from the
melt. The primary melts containing the alkali
metal oxides (sodium and potassium, sometimes
lithium), alkaline earth metal oxides (mainly cal-
cium and magnesium), or boron components act
as fluxes that dissolve the refractory batch com-
ponents. Gas solubility in the melt decreases
with increased dissolution of the refractory com-
ponents, leading to bubble trails. The bubbles
contain CO2 , N2 , O2 , SO2 , Ar, water vapor, or
combinations thereof.
Dissolution of refractory batch components,
the most important being coarse sand grains and
alumina raw material, slows down as the melt be-
comes nearly saturated, and a viscous melt with
only a small fraction of nonmolten material ap-
pears at ca. 1150 – 1250 ◦ C. The remaining re-
fractory batch components will dissolve at fur-
ther temperature increase. The batch slowly be-
comes transparent but remains chemically inho-
mogeneous. Blisters (bubbles) and cords (inho-
mogeneities in the melt) are particularly promi-
nent at this point. Removal of dissolved gases
and bubbles and finally resorption of residual
seeds (small bubbles < 0.2 mm) characterize the
next stage. The rate of melting depends on batch
composition, particle-size distribution, temper-
ature, and amount of cullet used.
The removal rate of gases from the melt de-
pends on the kind and amount of active fining
agent added to the batch and the redox state of
the melt, which often determines the tempera-
ture of fining-gas release and the quantity of gas
produced by the fining agent. These gases will
diffuse into small seeds, which grow due to this
gas infiltration. The bubble ascension rate in the
melt is proportional to the square of the bubble
diameter. The dilution of the gases in the bub-
ble with fining gases cause not only the fining
gases but also the other dissolved gases in the
melt to diffuse into the growing bubbles. Fin-
ing gases include sulfur dioxide, oxygen, and
sodium chloride vapor. During cooling of the
melt the residual fining gases can be resorbed
by the melt, since their solubility increases with
decreasing temperature.
Blisters, seeds, and cords, already de-
tectable by refractive index variations of around
5 × 10−4 , are removed in the fining and homog-
enization stage. Blisters and seeds are ≥ 0.2 and
0.2 – 0.05 mm in diameter, respectively. The use
of fining agents is reviewed in [126]. Consider-
able attention is required in glass manufacture
to make the melt blister-free by both expulsion
of gas bubbles (fining) and subsequent resorp-
tion of residual small seeds during controlled
cooling of the melt (refining). Blisters can arise

from several sources, including the type of raw
material used, the tank atmosphere, reactions
in the boundary layer between melt and refrac-
tory lining, electrochemical reactions in electri-
cally heated furnaces, electrochemical reactions
in refractories containing polyvalent ions such as
iron and titanium, air seeping through the tank
structure, or mechanical operations (e.g., stirring
or gobbing). Methods for fining are:
– Addition of chemical fining agents to the
batch
– Raising the tank temperature, with attendant
decrease of melt viscosity and increase of
bubble expulsion
– Lowering the temperature in the working end
and thus increasing gas resorption
Homogenization is carried out by:
– Blowing air or water vapor into the bottom
of the tank through bubbling pipes.
– Mechanical stirring or acoustic homogeniza-
tion.
– Applying a certain temperature profile in the
combustion chamber along the length of the
furnace. A hot spot in the central part causes
free convection flows in the melt and thus
improves mixing and heat transfer. A well-
developed spring zone in the central part of
the tank may prevent short-cut glass-melt
flows along the relatively cold melting tank
bottom.
Sodium sulfate and arsenic and antimony ox-
ides are generally used as fining agents. Only the
pentavalent arsenic and antimony compounds
produce oxygen as a fining gas at high tem-
peratures. Therefore arsenates or antimonates
are used in the batch, or nitrates are added to
oxidize the trivalent arsenic or antimony com-
pounds during melting. Nitrates produce oxy-
gen between 500 and 900 ◦ C [142]. Antimony
oxide, in combination with arsenic trioxide and
nitrates, is used in the production of optical
glasses. Other, less important fining agents in-
clude fluorides and, more rarely, chlorides and
bromides. Typically, ca. 0.3 – 0.6 wt % arsenic
oxide or arsenates is added to the batch, although
for some glass types up to 1.5 wt % arsenic triox-
ide may be employed. Antimony fining is used
for TV panel glass compositions and for sulfate-
free soda-lime glasses. Arsenic trioxide plus ni-
trates or arsenates is a widely used fining agent
Glass 61
for lead-containing glasses that are melted under
strongly oxidized conditions to avoid formation
of lead metal.
Above about 1350 ◦ C As2 O5 in the melt de-
composes into As2 O3 and oxygen, which is the
fining gas. During cooling below about 1300 ◦ C
the reaction is reversed. The fining mechanism
with antimonates is similar, but the pentavalent
antimony species dissolved in the melt decom-
pose at lower temperatures than As2 O5 , and oxy-
gen is released above about 1250 – 1300 ◦ C, de-
pending on the redox state (oxygen fugacity) of
the melt. An additional advantage of arsenic or
antimony is that oxygen gas bubbles which do
not combine with ambient gas bubbles in the
melt are resorbed at lower temperature because
of the back reaction from arsenic trioxide to ar-
senates or antimony trioxide to antimonates.
The low price of sodium sulfate makes it at-
tractive as a fining agent in commodity glasses.
It is, however, soluble only to ca. 1 wt % in most
melts and may lead to foaming or even sodium
sulfate droplets (sulfate gall) in the glass prod-
uct if used in excess. Sodium sulfate in oxiding
melts decomposes at above 1350 – 1450 ◦ C to
give SO2 and O2 as fining gases. During cool-
ing, bubbles containing both oxygen and sul-
fur dioxide can be resorbed. In reduced molten
glasses, sulfates react with reducing agents to
give SO2 gas at temperatures just above 1000 –
1100 ◦ C. This SO2 gas is the major fining gas
in these glass melts. Resorption of SO2 bubbles
in the absence of oxygen is limited, and only in
strongly reduced melts can SO2 or S2 bubbles be
resorbed due to formation of S2− in the melt. The
oxygen fugacity of the melt determines the tem-
perature at which sulfates start to decompose,
and the amount and kind of released gases also
depend on the redox state of the batch and melt.
5.4. Energy-Saving Technologies
The melting process requires relatively large
quantities of energy. The costs of energy con-
tribute 12 – 15 % to the total glass production
costs, depending on the country and type of
glass. Only about 25 – 55 % of the energy added
to the furnaces is used for heating the raw mate-
rial and for the endothermic reactions involved
in fusion of the raw materials into a melt. The
most important energy savings to be achieved
62 Glass
in industrial glass melting and glass production
focus on:
1) Improvement of the thermal insulation of
glass furnaces by using high-quality refrac-
tory materials for the glass-melting tank and
superstructure, allowing higer temperatures
inside the furnace.
2) Combustion control to avoid excess air in the
combustion chamber.
3) Reclaiming of energy from the waste gases
by extra air preheating or batch or cullet
preheating. In Western Europe some con-
tainer glass furnaces are equipped with cul-
let preheaters or mixed cullet/raw material
preheaters, which recover 10 – 20 % of the
energy from the gases and return it into
the furnace. There are different types of
batch/cullet preheaters: direct contact pre-
heaters (no physical separation between flue
gas and raw materials); indirect contact pre-
heaters (different channels for flue gas and
raw materials), and cullet preheaters with
electrostatic fields for capturing flue gas dust
particles.
4) Using oxygen instead of air, which reduces
the flue gas volume flow.
5) Improving control of glass melt viscosity in
combination with new forming techniques to
manufacture lightweight glass products.
6) Application of new furnaces, improving the
heat transfer to and in the glass melt (e.g.,
Sorg LoNOx melter).
5.5. Glass Cooling
During cooling, a melt is transformed from a
viscous fluid into a viscoelastic material and
eventually into a brittle substance. These grad-
ual transformations are accompanied by large
changes in properties.
High residual stress can be generated dur-
ing the transition from a melt to a cooled
glass. The magnitude of such stresses depends
largely on the cooling rate within the tempera-
ture range of the transformation from a liquid
into a rigid state, the coefficient of linear ex-
pansion of the glass, the thickness of the glass,
and the glass homogeneity. Annealing by con-
trolled cooling between the so-called annealing
point (viscosity 1012.4 Pa · s) and strain point
(1013.6 Pa · s) reduces residual stress to an ac-
ceptable level. The upper stress release temper-
ature (Section 4.1.1) corresponds to a glass vis-
cosity of ca. 1012.4 Pa · s or a stress release time
of 15 min with a gradient of 40 ◦ C/min. The
lower stress anneal temperature (strain point)
corresponds to a viscosity of 1013.5 Pa · s or a
stress release time of 15 h.
Determination of the time required to release
stress at a certain temperature requires measure-
ment of the viscosity. This is not practical in the
region of the stress release temperature. In prac-
tice, stress in the cold glass is measured optically
as the retardation of polarized light in a stressed
medium and expressed in units of nanometers of
retardation per centimeter of material.
Glass is amorphous and therefore isotropic;
its properties are often the same in all directions.
However, under compressive or tensile stress
anisotropic behavior appears, and the glass be-
comes birefringent. The applied stress deforms
the polarizable (an)ions within the glass (pre-
stressed electron cloud), which results in a dif-
ferent velocity of light transmission in one po-
larization direction as opposed to the other. A
phase shift D appears, depending on the glass
thickness and the stress present. This phase shift
is is generally expressed per unit of glass thick-
ness; usually 1 cm: D/d = C · s, where D is the
phase shift in nm, s the stress in Pa, C the stress-
optical coefficient or Brewster’s constant, and d
the glass thickness in cm. Some values of C (in
nm cm−1 Pa−1 ) follow:
Soda-lime glass 0.27
Borosilicate glass 0.40
Quartz glass 0.34
3 PbO · 5 SiO2 0
Due to this birefringence phenomenon,
stresses in glass can be measured by using a
polarizing microscope. Monochromatic light is
polarized by a polarizer. Because polarizer and
analyzer are perpendicular to each other, no light
is transmitted. When a birefringent material is
placed between polarizer and analyzer at an an-
gle of 45◦ , the two components of the beam of
light – one parallel and the other perpendicular to
the stress direction – are transmitted with differ-
ent velocities through the material (retardation
of polarized light in the direction of compressive
stress), resulting in a difference in phase. Then

after passing through the sample, the two light
beams interfere with each other. If the phase shift
is equal to 1/2λ, (1 + 1/2λ), etc., the composite
beam vibrates in the direction of the analyzer
and therefore is transmitted. If the phase shift
equals λ or a multiple thereof, the composite
beam vibrates perpendicular to the analyzer and
is extinguished. The stress release viscosity is
determined from the required stress retardation
time t by using the following formula:
Ds = D0 + CA−1 t−1
where D0 is the original retardation caused
by the stress, and Ds the retardation after time
t, both expressed in nanometers per centimeter;
A is the cooling constant; and C is the Brewster
constant of the glass.
Residual stresses, expressed as maximum re-
tardation of polarized light in the stressed glass,
of the order of 100 – 200 nm/cm remain in the
glass after cooling. The geometry of the article
and glass composition affect the cooling process
and hence the amount of residual stress. Table-
ware is cooled at such a rate that residual stress is
less than 50 nm/cm; optical glass requires slow
cooling to keep residual stress below 10 nm/cm.
Figure 36 shows a recommended temperature –
time curve for the cooling of a glass article.
Figure 36. Annealing and cooling of a glass article (tube)
with a diameter of about 10 cm and a wall thickness of 1 cm
The annealing temperature is about 530 – 540 ◦ C, and the
strain point about 500 ◦ C
5.6. Heating and Regulating Glass Melts
Natural gas, fuel oil, or electricity is used in most
glass melting units. Radiation directly emanat-
ing from the flame and reflection from the crown
Glass 63
into the melt are the principal processes of heat
transfer in fossil-fuel-fired melters. Iron in the
glass, especially in the iron(II) state, increases
the IR absorption and the transparency of the
melt for IR radiation decreases with increasing
content of iron(II). Glass melts for products like
tinted float glass and green or amber container
glass show limited transmission of the IR radi-
ation from the crown and flames. Extra convec-
tion or electric boosting in these glass melts is
necessary to provide heat to the bottom section
of the melting tank. Production of glass that ab-
sorbs strongly in the infrared requires a shallow
bath, electrodes, or bubbling to maintain a suf-
ficiently high temperature at the bottom of the
pool.
Preheated air is injected into the combus-
tion chamber in most furnaces. Both recuper-
ative and regenerative preheating can be used.
Recuperative preheating entails countercurrent
or cocurrent heat exchange from the flue gases
to the combustion air in a metal heat exchanger,
the so-called recuperator. Often the flue gases
flow through the core of the recuperator while
air flows through the mantle of the twin shell
recuperator or through tubes positioned in the
flue gas channel of the recuperator. About 25 –
35 % of the flue gas heat can be transferred to the
combustion air in such recuperators. Small glass
tanks and tanks used for glass-fiber manufacture
tend to operate with this system.
Regenerative preheating involves a discon-
tinuous process that originated in the steel in-
dustry. Here, air is blown before combustion
through a refractory brick chamber, which is it-
self heated by the flue gas. In this cyclic pro-
cedure, during a period of 20 – 35 min air is
preheated to 1200 – 1350 ◦ C in one regenerator,
and the flue gases preheat the bricks (piled as a
checkerwork) in another regenerator at the same
time. The exhaust gases are cooled from about
1450 to 550 ◦ C, transferring about 60 – 65 % of
their sensible heat to the refractory bricks. After
this period, the preheated regenerator is used for
combustion air preheating, and the other regen-
erator is heated by flue gases.
The temperature in the melting tank and in the
refractory walls is measured by Pt – Pt – Rh ther-
mocouples embedded in zircon, AZS, or chrom-
mium oxide refractory blocks and positioned
about 5 cm deep in the vault of the tank. Some
64 Glass
thermocouples are positioned in the melt, for ex-
ample, just before the melt enters the throat. Ide-
ally, this temperature is constant and must be
controlled; the set point for this thermocouple
depends on melting load and glass color.
Thermocouples in the refractories of the
crown or positioned in the combustion chamber
just below the crown measure the combustion
chamber temperatures, and temperature profiles
in the combustion chamber are controlled to
avoid damage to the crown and to achieve the
required temperature profile in the melter.
Optical pyrometers are used to measure tem-
perature along the walls of the tank or the tem-
perature of the metal-line. Melt viscosity is
not monitored but inferred from the estimated
melt temperature, although some feeders are
equipped with on-line viscosimeters to control
glass melt viscosity prior to delivery to the form-
ing process. Platinum-sheathed thermocouples
are used in the melting end and before the melt
enters the forming cycle. The temperature of the
regenerator is also monitored with thermocou-
ples. Tank pressure is kept within ± 0.04 kPa
of ambient pressure and is measured by metal
membrane manometers located below the fur-
nace in the superstructure. Flue gas blowers or
valves are used to control the pressure. To avoid
leakage of flames or gases to the ambient air
through the joints, a furnace pressure slightly
lower than ambient pressure is preferred.
Sensor electrodes, optical laser reflection sys-
tems or nuclear radiation level devices measure
the glass melt level. Changes in glass melt level
are corrected by changing the batch charging
rate.
The four principal variables that must be
monitored during melting are the flows of natural
gas or fuel oil and combustion air, batch charging
rate, and temperatures in the melt and combus-
tion chamber, all of which are kept constant for
specific melt and fining temperatures. Standard
technical gas analyzers or zirconia/platinum-
based oxygen activity sensors are used to control
the intake of fresh air and the composition of flue
gases.
5.7. Refractory Lining of Melting Units
The three criteria for selecting refractory mate-
rials are: required lifetime, potential glass de-
fect rate, and cost per amount of glass pro-
duced. To obtain an idea of the amount of refrac-
tory material required, consider a medium-size,
130-t/d tank with regenerative heating. Con-
struction of such a tank requires 460 t of fire
clay, 175 t of fused-cast tank bricks, 104 t of
chrome magnesite (MgO · Cr2 O3 ) or magnesia –
alumina spinel refractories, 112 t of magnesite
or forsterite (Mg2 SiO4 ) bricks, 100 t of silica
bricks, 9 t of zircon (ZrSiO4 ), and 2 t of unspec-
ified lining material. Tank blocks poured from
refractory melts are increasingly used as lining
material in large glass tanks to improve contact
between melt and lining material and to prevent
problems with stones and cords in the final prod-
uct.
The most widely applied refractory material
for glass melting tanks is fused cast AZS pro-
duced from a melt of alumina, zircon (zirconia
silicate), and small amounts of fluxing agents
like soda. The AZS melt is poured in sand molds
at temperatures exceeding 2000 ◦ C. The sand
molds containing the cast material are cooled
very slowly to avoid thermal stress and forma-
tion of cracks. The refractory fused cast blocks
must be post-treated to achieve the desired di-
mensions and to remove parts which contain
voids caused by contraction during cooling.
A more recent development is the use of
fusion-cast 96 % ZrO2 blocks, a refractory ma-
terial more expensive than conventional blocks.
These are used only in those parts of the tank that
are particularly susceptible to corrosion. The use
of these blocks in melting tanks for the produc-
tion of high-quality glasses like TV panel glass
reduces the defect level in the final products.
Chemical considerations limit the choice of
lining material. The most common materials
used are silica, alumina, or zirconia, or combina-
tions thereof. Linings containing sintered chro-
mium oxide are used in the production of some
specialty glasses like E glass for continuous fila-
ment fibers. The high price of tin oxide prevents
its use in normal applications. Magnesium ox-
ide dissolves in the glass melt and can therefore
only be used in the regenerator or parts of the
combustion chamber.
The crown of most glass furnaces is made of
silica with very low amounts of residual quartz
and with > 97 wt % SiO2 . For higher crown tem-
peratures or aggressive gas atmospheres, the
more expensive mullite, AZS (special quality

with a low fraction of silicates), or fusion-cast
alumina refractories are used. The sidewalls of
the combustion chamber are constructed from
fusion-cast AZS, chromium oxide, and silliman-
ite or mullite for some kinds of glasses. Zircon
refractories are applied between AZS and silica
to avoid a direct reactive contact between silica
and AZS. An overview of the refractory materi-
als used is given in Table 27.
Glass melts tend to wet platinum (electrodes,
stirrers, feeder elements, bushings) and molyb-
denum (electrodes). Caution is needed in us-
ing these materials in melts because some glass
compositions and low or very high oxygen fu-
gacity will corrode them. The vault of a tank
is usually lined with silica, although its chem-
ical resistance is not particularly good in spe-
cific temperature regions. The corrosion prod-
ucts of silica are soluble in the melt, however,
and hence do not significantly affect melt com-
position. Melting products derived from silica,
especially those resulting from reactions with
sodium vapors from liquid sodium silicates, can
react with the AZS sidewall refractories forming
alumina-rich sodium silicate melts with some
baddeleyite (ZrO2 ) crystals or dissolved zirco-
nia. These melts dripping into the melting tank
can form knots and recrystallized components
like secondary baddeleyite in the glass products.
The refractory lining of the tank and super-
structure is 250 – 350 mm thick and covered by
additional refractory layers. These layers pro-
vide thermal insulation, and the requirements are
different to those of refractories in direct contact
with the melt or furnace atmosphere. Insulat-
ing refractory bricks often show a high porosity.
Typical insulating refractories are made of alu-
minum silicates like chamotte and sillimanite.
Patch is used to seal the joints to avoid leakage
and cold condensation spots. The tank refracto-
ries at the position of the metal line are not co-
vered by insulation layers. The refractory blocks
at melt-line level are often cooled with air from
the outside to reduce the rate of attack by the melt
at these positions. Melt-line corrosion is caused
by microconvection of the glass melt at the sur-
face due to surface tension gradients of the melt
close to the slowly dissolving refractory. Micro-
convection removes the protecting diffusion bar-
rier formed between the melt and the refractory
material. This microconvection becomes slower
at lower temperatures.
Glass 65
5.8. Vapor-Deposited Glasses
Vapor-deposited glasses are discussed with opti-
cal waveguides (see → Fiber Optics, Chap. 3.5.).
The process is also of interest for specialty
glasses (for instance for optical fibers) that re-
quire extremely high purity or are prone to liquid
immiscibility in conventional melting. All vapor
deposition processes use volatile halides (e.g.,
SiCl4 or BCl3 ) or metal chelate compounds.
Rare earth organic chelates are used as additives
in laser optics. These gases/precursors are pro-
cessed to provide bulk high-purity oxide glasses.
The pure halides are entrained in a carrier gas
(oxygen) at < 323 K and react at > 1773 K. Re-
action of the halide with oxygen results in con-
densation of a finely divided oxide powder on the
substrate. The high-purity, inclusion-free pow-
der has a surface area of about 20 m2 /g, which
provides a sufficiently powerful drive for rapid,
thermally activated (using flames, microwave, or
plasma techniques), viscous sintering. Examples
of glasses manufactured in this way are Corning
Code 7943 and 7940.
5.9. Occupational Health
The principal health concerns in the glass in-
dustry have been reviewed [127–129]. The po-
tential hazards specific to this industry include
silica, lead, arsenic, antimony, asbestos, barium,
chromium and other heavy metals. Heat stress,
noise, and IR radiation must also be addressed.
Other factors of concern are particulate and NOx
emissions from furnaces. Firing under reducing
conditions may lead to excessive CO formation
in the furnace. Most of the CO is oxidized to
CO2 in the flue gases, but those working in the
vicinity of poorly sealed furnaces must be aware
of health or poisoning risks. Three control mea-
sures are recommended to deal with the hazards
associated with glass manufacture:
1) Engineering controls that include confine-
ment, automation, and isolation in handling
raw materials; batch room ventilation; and,
whenever possible, substitution of question-
able chemicals by harmless ones; batch han-
dling is preferably carried out in closed
Table 27. Refractory materials used in glass furnaces

66
Refractory Composition, wt % Apparent Density, Maximum use Linear thermal Use
porosity, g/cm3 temperature, expansion, %
◦
ZrO2 Al2 O3 SiO2 MgO Cr2 O3 Other vol% C at 982 ◦ C at 1316 ◦ C

Fused cast
ZB-X950 94 0.8 4.5 0.7 5.41 0.70 a 0.45 b glass contact

Glass
0.4 (Na2 O)
AZS 33 – 41 46 – 50 12 – 16 0.8 – 1.8 1 3.8 – 4.1 1650 0.90 0.94 glass contact,
(Na2 O) superstructure
Corundum- 32.5 – 40 45 – 51 12 – 16 1.1 – 1.5 3.77 – 4.09 0.70 a glass contact,
Zircon (Na2 O) superstructure
α-Alumina 99 1.1 1870 0.77 1.05 superstructure,
crown
β-Alumina 94 – 95 5 – 6 (alkali) 4.1 >1650 0.65 0.85 breastwall,
arches, crowns
95 1 4 (alkali) 2 1870 0.73 1.05 fiberglass
α,β-Alumina furnace throats
Alumina – 60 – 61 1.5 – 2 6 27 – 28 4 – 5 (Fe2 O3 ) 4.2 >1650 0.76 1.13 refiner or
chrome channels
Chrome – 4–5 1–2 8–9 79 – 80 6 – 7 (Fe2 O3 ) 4.9 >1650 0.71 0.97 textile
spinel fiberglass
(high ware
areas)
Bonded or
sintered
Dense 64 – 65 33 – 34 0.5 4.22 1650 0.39 0.60 high-duty
zircon glass contact
Medium 65 – 66 33 – 34 11 3.92 1650 0.48 0.73 channels,
dense zircon refiner,
forehearth
Sintered 65 – 66 33 – 34 16 – 28 3.39 – 3.76 1650 0.45 0.62 melting and
zircon refiner
bottoms
Sintered 20 70 10 20 – 23 2.92 – 3.04 34 – 35 0.62 0.82 tubes, refiner
zircon AZS paving,
regenerator
target walls
Table 27. Continued

Refractory Composition, wt % Apparent Density, Maximum use Linear thermal Use

porosity, g/cm3 temperature, expansion, %
◦
ZrO2 Al2 O3 SiO2 MgO Cr2 O3 Other vol% C at 982 ◦ C at 1316 ◦ C

Dense 94 4–5 0 – 1 (TiO2 ) 1.6 3.44 1760 0.81 optical and

sintered lead glass
alumina tanks
Chrome – 81 16 3 0.76 1.13 fiberglass
alumina tanks
90 % 89 – 91 8 – 10 19 – 26 2.66 – 2.86 1750 0.69 1.04 superstructure
alumina brick
Chrome 96 4 (TiO2 ) 18 4.06 > 1650 0.74 1.16 fiberglass
onide tanks
Mul- 60 – 80 18 – 37 1–6 14 – 24 2.24 – 2.59 1650 – 1700 0.58/0.62 0.81/0.93 backwalls,
lite/silimanite breastwalls,
bottom
checkers
Fireclay, 37 – 45 57 – 50 6 – 22 2.05 – 2.42 1400 0.38/0.56 0.62/0.75 day tanks or
bricks and flux non-
continuous
furnaces,
sidewall
insulation
Superduty 96.3 2.9 (CaO) 20 – 24 1.84 1590 – 1650 crown
silica brick
Fused silica 98 – 99 1.2 11 – 15 1.87 – 1.94 1650 burner blocks,
brick thermocouple
tubes, crown
Insulation 34 – 36 56 – 58 6 – 10 63 – 77 0.67 – 0.86 1090 – 1430 0.43 0.60 outer
brick (I.F.B.) insulation
Glass
67
Table 27. (Continued)

68
Refractory Composition, wt % Apparent Density, Maximum use Linear thermal Use
porosity, g/cm3 temperature, expansion, %
◦
ZrO2 Al2 O3 SiO2 MgO Cr2 O3 Other vol% C at 982 ◦ C at 1316 ◦ C

Basic
refractories

Glass
High MgO 98 1 – 2 (CaO) 17 – 22 2.77 – 2.88 >1760 1.31 1.81 refractory
brick checkers
8.3 88.5 3–4 22 2.77 >1760 1.05 1.50 refractory
Spinel-bonded checkers
magnesite
Magnesite 4.1 93.6 2–3 20 2.78 1700 1.31 1.81 refractory
brick checkers
Forsterite 10.9 29.5 50.3 22 2.62 >1650 1.10 1.39 refractory
brick checkers
Dense 95 4 (TiO2 ) 18 4.06 >1650 0.74 1.16 fiberglass
chromic oxide furnace throats
Chrome 15 – 34 3–6 14 – 19 22 – 28 11 – 17 18 – 25 2.88 – 3.36 1650 0.81 1.11 lower zone
brick (Fe2 O3 ) refractory
checkers
Chrome – 16 – 27 4–8 27 – 53 12 – 28 8 – 14 14 – 25 2.56 – 3.26 1540 – 1650 0.86 1.19 regenerator
magnesia (Fe2 O3 )
brick
Chrome – 81 16 3 0.76 1.13 fiberglass
alumina tanks
Unichrome 59 29 1.0 4.2 2 (Fe2 O3 ) fiberglass
tanks
a
Linear thermal expansion at 1000 ◦ C.
b
Linear thermal expansion at 1500 ◦ C.

spaces with baghouse filters to prevent dust-
ing during filling or discharging of the silos.
2) Administrative controls, including job ro-
tation, education, safety instructions and
proper work practices.
3) Use of personal protective equipment, in-
cluding respiratory protection, proper cloth-
ing, and hearing and eye protection.
In the United States, OSHA has established
the right of employees to be informed of the po-
tential hazards of materials in their workplace.
This organization also requires that producers
of hazardous materials determine the potential
health and physical hazards of such materials
and transmit this information to the consumer.
Among the standard reference works on indus-
trial hygiene is Patty’s Industrial Hygiene and
Toxicology [130]. For most toxic components
limits have been set for levels in ambient air. Pro-
cedures and instructions for handling toxic ma-
terials or flammable and explosive components
are often part of ISO 9002 or other standardized
practices in modern glass factories.
6. Forming
The shape of a piece of hot glass (temperature
above T g ) can be changed by an external force
which causes viscous deformation. In the known
forming techniques the external force is applied
by:
– Drawing (fiberglass, flat glass, tube glass)
– Blowing (container glass, bulbs)
– Pressing (tableware, container glass, TV pan-
els)
– Centrifuging (insulation glass wool)
– Rolling (wired glass, figure glass)
– Casting
In some cases, these processes are combined.
The degree to which the glass is transformed
depends on the magnitude of the force and the
prevailing glass viscosity. A low viscosity im-
parts a high rate of deformation. After the form-
ing process a high viscosity is required, so that
the product retains its shape (viscosity of about
107 Pa · s, softening point). During forming, the
glass should be cooled down precisely to achieve
these conditions. The degree of cooling depends
on the heat content of the glass product and the
Glass 69
rate of production (contact time in the mold).
Large products with a high heat content can
not be formed as fast as smaller products. Most
forming processes take place at a viscosity of 102
to about 104 Pa · s (working range). The work-
ing temperature is defined as the temperature at
which the melt has a viscosity of 103 Pa · s. Dur-
ing forming, the glass melt cools and the vis-
cosity increases. With increasing viscosity, the
required transforming force increases, and the
deformation rate will decrease. Viscosities and
temperatures for some forming techniques are
listed in Table 28.
Table 28. Deformation and forming methods for different glass
products
Process Viscosity, Pa · s Temperature,∗
◦
C
Drawing, centrifuging 102 1200
Fast pressing 103 1050
Fast blowing 104 900
Slow pressing 105 800
Slow blowing 106 750
Form becomes rigid (or 107 700
stable)
∗ For soda-lime glass.
Most of today’s forming methods have their
origin in the use of the blowpipe, invented by the
Romans and reaching the pinnacle of expression
with the Venetian glassblowers of Murano.
Molten glass is pressed, blown, drawn, rolled,
poured or quenched, depending on the desired
shape and intended use. Bottles, dishes, optical
lenses, and television tubes are formed by blow-
ing, pressing, casting, or spinning glass against
a mold to cool it and set its final shape. Win-
dow glass is made by floating the glass melt
on a molten tin bath; tubing rods and optical
fibers are made by drawing the glass in air until
it sets and can be cut to length. Frit glass, some
of which is intended to be crushed into pow-
der, is quenched between water-cooled rollers
or ladled directly into water and then dried (dry-
gauged). Tube glass is drawn from the melt by
conducting the melt through a feeder opening
on a sloped or vertical rotating mandrel (blow-
pipe). The glass distributes itself along the cylin-
drical surface of the mandrel and is drawn out
into a tube. The mandrel consists of a hollow
ceramic cylinder through which air is blown.
This air flows through the resulting glass tube,
which is released from the mandrel. Mandrel
70 Glass
size, air pressure and drawing speed and glass
melt viscosity determine the dimensions of the
glass tube. Art glass is often hand-formed by free
blowing and shaping while soft. These forming
operations all require a melt cooled to a charac-
teristic viscosity of between l02 and about 104
to 105 Pa · s, generally at 800 – 1400 ◦ C (depend-
ing on glass type), as shown in Figure 13.
6.1. Hand Forming
Some industrial forming methods derive from
hand-forming techniques and are therefore dis-
cussed in some detail here. The major break-
through in glass production was the invention of
the blowpipe by the Romans. The flexibility of
this technique still makes it popular in fabricat-
ing complex specialty items. The blowpipe is a
hollow stainless steel pipe. A gob of glass is col-
lected at the end of the pipe by dipping it into
the melt. Blowing air through the pipe results
in swelling of the gob, provided the viscosity
of the glass is still sufficiently low, reheating is
necessary if the viscosity becomes too high.
The Rhenian technique uses a blowpipe with
a conically thickened end. The glassblower gath-
ers the appropriate amount of glass melt from the
working end of the furnace or the pot and col-
lects the glass on the end of the blowpipe, and
the gob is cooled by rotation in a bowl-shaped
wooden form or on a metal plate until the vis-
cosity required for blowing is reached. The gob
is then placed in an iron or wooden mold and
blown to the shape of the mold.
In the Bohemian technique, a straight blow-
pipe is used. A gatherer, who collects the gob on
the pipe, and the glassblower work in concert.
The gatherer collects a small amount of glass
on the end of the pipe and blows a small sphere
with dimensions prescribed by those of the final
product. The glassblower takes the pipe from
the gatherer, dips it again in the oven, collects as
much glass as needed for the final product and
blows it to the shape of the mold.
6.1.1. Blowing
The hand-forming operations described above
immediately suggest a way of automating a
glass-forming process by blowing gobs of the
proper viscosity into molds. Many products are
indeed made by variations on this theme, as sug-
gested by the names of the various techniques:
blow, blow-and-blow, puff-and-blow, and press-
and-blow processes.
Deep items (e.g., bottles, jars, and light-bulb
envelopes) are formed by blowing glass into
molds with air pressure, as shown in Figure 37.
Hinged molds, which can be opened to remove
the ware, are generally used for the blowing op-
eration. Articles with circular cross section are
blown into hinged paste molds. These molds are
lined with a water-absorbent coating or wetted
cork, which develops a steam cushion between
the coating and glass during blowing, allowing
the glass to be rotated in the mold. A second type
of mold is the hinged hot-iron mold used for the
manufacture of ware with noncircular cross sec-
tion. Here, the glass comes directly into contact
with the mold surface on blowing. The surface
quality of articles blown into hot-iron molds is
inferior to that of paste molds. Hot-iron molds
are used for ware of any shape, in particular for
screw threads, multiple decoration, or raised let-
tering.
Figure 37. Forming by blowing
A) a) Empty mold; b) Blank ready for blowing; c) Blank
blown out; d) Untrimmed piece; e) Finished piece
B) a) Empty mold; b) Blank ready for blowing; c) Blank
blown out; d) Untrimmed piece; e) Finished piece
Narrow-mouth containers are manufactured
in a two-stage, blow-and-blow process (Fig. 38).
The gob is delivered to a blank mold, where a
settle blow and a counter blow form it into a
blank. This blank is then transferred to a blow
mold, where it is blown into its final shape.

Figure 38. Forming by the blow-and-blow process
a) Delivery; b) Settle blow; c) Counter blow; d) Transfer
from blank mold to blow mold; e) Reheat; f) Final blow
with internal cooling; g) Takeout
The Corning ribbon machine is the classical
example of mechanized glass-forming processes
(Fig. 39). The machine is used to manufacture
simple seamless products, such as light bulbs
(1200/min), flash-bulb envelopes (2000/min),
and Christmas tree ornaments. A puff-and-blow
method is used in which a glass ribbon 50 mm
thick is formed at about 1080 ◦ C by two rollers.
The lower roller has small indentations, which
form small circular thicker regions in the glass
ribbon. Transport of the ribbon brings the thick-
ened regions above a hole. The glass sinks into
the hole and is blown out by blow-heads that
move synchronously with the ribbon. The turret
chain machine is used for larger articles. This
device also uses the puff-and-blow method but
Glass 71
with individual glass gobs rather than a ribbon,
thereby reducing the amount of cullet.
So-called gobs are delivered by the feeders of
the glass furnace by shears cutting portions of a
certain weight from a flow of glass melt. These
gobs are conducted to the blowing machines.
Blowing machines for bottles in use today in-
clude the Lynch-10, capable of delivering 25 –
80 pieces per minute with bottle weights of 30 –
600 g; the Roirant-R-7, delivering 20 – 80 pieces
per minute at weights of 100 – 1200 g; and the
Hartford-IS-12, now manufactured by Emhart
and Maul and used almost universally, which op-
erates with the blow-and-blow process and pro-
duces about 10 pieces per minute. There are IS-
6, IS-8, IS-10, IS-12 forming machines supplied
by several machine manufactures; the number
stands for the number of sections in series per
machine. In each section 1, 2, or 3 gobs are si-
multaneously formed into a jar or bottle. A IS-8
machine with 3 gobs per section may produce
more than 250 bottles per minute with a weight
of about 200 g per bottle. Today, even larger ma-
chines are used for mass production.
6.1.2. Pressing
The role of air in blowing glass is taken over
by a plunger (male half of the mold) in press-
ing glass. Blowing is used in the manufacture
of deep items, whereas pressing is used particu-
larly for relatively flat items such as dinnerware,
optical and sealed-beam lenses, filter glass, or
television tube panels. The press mold consists
of three parts: the mold bottom, the plunger, and
the ring; the latter functions as a seal between
the other two parts. In hand pressing, molten
glass is gathered on a solid steel rod punty (pon-
til) and drips into the mold bottom. A pair of
shears severs the glass remaining on the punty
from that in the mold. The plunger is then forced
into the mold, causing the glass to flow into the
space between plunger and mold. Movement of
the plunger ceases when the space is filled. The
plunger is withdrawn and the pressed glass re-
moved from the mold. Three types of molds used
for pressing are shown in Figure 40.
The principles of machine pressing are simi-
lar to those of hand pressing. For instance, a set
of molds, commonly made of cast iron, bronze
steel, or superalloys with galvanized surfaces,
72 Glass
Figure 39. The Corning ribbon machine
a) Water cooled rollers; b) Glass ribbon; c) Blow heads; d) Rotating paste molds; e) Blow box; f) Mold-closing cam; g) Mold-
opening cam; h) Glass bulbs; i) Stripper; j) Crack-off bar; k) Conveyor for removing product
is mounted on a circular, horizontally rotating
press table. Typically 8 – 16 mold positions lie
on the periphery of this table. Glass flows from
the refining end or feeder into a refractory bowl
with a circular hole (spout) in the bottom. A re-
ciprocating plunger of refractory material above
this hole causes the glass to be extruded in
pulses. Extruded glass is separated into gobs of
the proper volume by a pair of shears directly
below the hole. The motions of reciprocating
plunger, shears, and press table are synchro-
nized, ensuring that the gobs fall into succes-
sive molds. The plunger of the pressing process
descends and presses the gob into the desired
shape. The glass is usually cooled by blowing
air against it. The hollow plungers are cooled
separately by circulating coolant.
Mold temperatures must be monitored; glass
may adhere to a mold that is too hot or have a
wrinkled surface if the mold is too cold. A rub-
bering compound like a graphite suspension is
applied to the mold, plunger, and ring to prevent
adhesion of glass to the mold.
The pressing speed is determined by thermal
conductivity, temperature, and temperature dis-
tribution. Normal pressing temperature is 670 –
800 ◦ C; the lower limit is determined by the sha-
peability of the glass; the upper, by the oxidation
resistance of the mold.
6.1.3. Blowing Combined with Pressing
In blowing and pressing, the gob is first pressed
in a blank mold followed by transfer of the
blank or parison to the blow mold. The blank
is blown to its final shape in this second mold
by a blow-head set over the neck (Fig. 41). For
modern mass production IS machines with 10 –
16 sections are used to make press-blow items
with wide necks (jars) and narrow necks (narrow
neck press blowing) at high production rates.
In each section two or three jars or bottles are
produced. Generally, press-and-blow forming
processes give a more uniform and more con-
trollable glass distribution during forming than
blow-and-blow processes. For bottles and jars
press-and-blow processes allow smaller weights
per item, while still obtaining sufficient mechan-
ical strengths.
6.1.4. Drawing
The three forming processes used to manufac-
ture glass tubing or rods are the Danner, Vello,
and Schuller process. The Vello process has
gained favor over the Danner process because
of greater flexibility.
In the Vello process, molten glass flows down-
ward through the annular space between a hol-
low vertical mandrel and a refractory or (noble)
metal ring set in the bottom of a special fore-
hearth, the bowl. Air blown through the man-
drel into the fresh glass tube maintains the di-
mensions of both bore and diameter. The soft
tubing, hanging in the shape of a catenary bet-
ween the end of the mandrel and the drawing
machine, is pulled onto a horizontal conveyor to
the cutting machine.
Diameter tolerance for drawn glass tubing is
typically 5 – 7 % for 6-mm tubing and 2 – 3 % for
150-mm tubing. Wall thickness tolerance is 11 –
15 % for the smaller diameter tubing and 12 %
for tubing of 100-, 125-, and 150-mm diameter.

Figure 40. Types of molds used for pressing
A); B); C); a) Empty mold; b) Loaded mold; c) Glass pressed;
d) Finished; e) Untrimmed
The Vello process can accommodate a wide
range of glass compositions and production rates
of > 45 kg/min with good dimensional control
for tube diameters up to 65 mm. With special
care, as required for thermometer tubing, the
standard deviation of the tubing diameter can
be held to 0.3 – 0.5 % of the nominal dimension.
The change in direction of the drawn tube
from vertical to horizontal in the Vello process
causes kinking in larger diameter tubes. A mod-
ification of the Vello process, the down-draw
process prevents this by drawing tubing up to
280 mm straight down from the bowl with good
dimensional control, while maintaining the pro-
duction rates and glass-composition flexibility
of the Vello process.
Rods can be drawn by any of the tube-
drawing processes by turning off the air flow
through the mandrel. The glass tube collapses,
Glass 73
Figure 41. Blowing combined with pressing
a) Delivery; b) Start of plunger pressing stroke; c) Full press-
ing stroke; d) Transfer from blank mold to blow mold; e) Re-
heat; f) Final blow with internal cooling; g) Takeout
and rods are then formed, rather than tubing.
The first mechanical drawing process for tubing
glass was developed by Danner (USA) in 1917
(Fig. 42). In this process the liquid glass flows
through a feeder opening on top of a downward-
sloping rotating (5 – 10 rpm) mandrel (blow-
pipe). The glass distributes itself along the cylin-
drical surface of the mandrel and is drawn out
into a tube. The mandrel consists of a hollow ce-
ramic cylinder through which air is blown. This
air flows through the resulting glass tube, which
is released from the mandrel. Depending on the
desired diameter of the glass tubes (1 – 70 mm),
mandrels are used with a diameter varying from
100 to 700 mm.
The tube dimensions can be adjusted by
means of the pressure of the compressed air and
the drawing speed. At constant drawing speed, a
higher compressed air pressure leads to a larger
74 Glass
tube diameter with a thinner wall thickness; a
larger drawing speed with constant compressed
air pressure results in a smaller tube diameter
and a thinner tube wall. By combining these con-
trol factors, tubes of different dimensions can be
manufactured with the same mandrel.
Figure 42. The Danner process
The consistency of the desired dimensions
strongly depends on a constant discharge of the
glass melt from the feeder and on a stable tem-
perature profile of the glass during both the dis-
charge of the melt from the feeder into the man-
drel and drawing into a tube. The viscosity of
the discharging glass melt from the feeder open-
ing should be about 102 Pa · s and at the end
of the mandrel the viscosity should be about
103.5 Pa · s. The drawing speed amounts to about
400 m/min. for glass tubing of 2.5 mm diameter
and about 100 m/min for 37 mm tube. The maxi-
mum production capacity of the Danner process
is about 40 t/d.
In the Schuller process, developed in Ger-
many in 1931, the glass tube is vertically drawn
upwards. There are several modified versions of
this process. The glass flows from the feeder into
a rotating refractory dish with a blow pipe in the
center at the bottom (cone). From this dish the
glass tube is directly drawn upwards. Around the
initial part of the glass tube a ceramic cylinder is
located that rotates synchronously with the dish
and which ensures a uniform temperature of the
glass melt while it is drawn upwards. The tube
dimensions are determined by the dimensions
of the cone, the compressed air pressure, and
the drawing speed. They can also be influenced
by means of the cooling air, which is blown from
holes in a cooling ring, located above the rotat-
ing cylinder. By using different blow pipes glass
tubes can be manufactured with a diameter rang-
ing from 3 to 50 mm. The production capacity
per machine is up to about 3 t/d.
6.1.5. Redrawing
In the redrawing process, glass first is formed
into the desired shape and subsequently re-
heated. The specific characteristic of this re-
drawing is that it preserves shape; e.g., a piece
of glass with a square cross section of centime-
ter dimensions can be redrawn into a long rod
with a square cross section with micron dimen-
sions. The topology-preserving character of the
redrawing process makes it ideally suited for
miniaturization and is the basis for all optical
waveguide technology.
6.1.6. Casting
Casting is a glass-forming process in which
melt is poured into a mold. The most spec-
tacular examples of cast products are telescope
mirrors for the space observatories, often made
from borosilicate glass; pieces larger than 5 m
in diameter and weighing more than 36 t have
been produced. Dimensional tolerances as low
as 0.1 mm can be achieved in this process. Cen-
trifugal casting is a variant of the casting process:
a gob of glass drops into a mold, which then spins
rapidly, spreading the glass by centrifugal force
over the inside of the mold (Fig. 43). Funnel-
shaped items, such as television tubes and mis-
sile radomes (nose cones), are formed by this
process.
Figure 43. Centrifugal casting of television tubes
a) Mold glass; b) Distributor; c) Ejector valve; d) Grooving
disk

6.1.7. Fritting
Fritting involves quenching a melt to cre-
ate a highly thermally stressed glass that can
be crushed easily in a ball mill. The glass
is quenched between water-cooled rollers or
poured into water. The former method is advan-
tageous because it produces a thin friable ribbon
that often gives more uniform mill feed.
6.1.8. Flat Glass Forming
6.1.8.1. Pilkington Float Process
Flat glass manufacture was revolutionized in
the late 1950s by the invention of the Pilk-
ington float process. This process has made
other flat glass manufacturing processes (e.g.,
the Libbey – Owens, Fourcault, and Pittsburgh
processes) obsolete. In the older processes, the
glass sheet is pulled vertically through a slotted
draw bar by the action of a pair of rolls contact-
ing the glass melt sheet (Fourcault), or the glass
is pulled over a bar. In the Pittsburgh system the
glass is pulled upwards between pairs of rotat-
ing rolls after passing across a solid drawing bar.
At the same time, the glass sheet is cooled by
the draught created within the machine, which
is about 13 m high. The maximum capacity of
these machines is 50 t/d. Up to ten machines per
furnace have been realized, resulting in a fur-
nace capacity of about 300 t/d. This process still
is being used in Eastern European countries and
in the developing countries because of the rela-
tively low investment costs.
In a similar system, developed by Libbey –
Owens, the glass is also pulled vertically from
the furnace. However the glass ribbon is bent
across a bending roll at a height of about 1 m
from the surface roof and subsequently pulled
over a horizontal roller conveyor through a cool-
ing zone. This process and the Fourcault process
are still being used for thin glass (≤ 0.4 mm), for
optical applications, and for LCD-displays.
In float glass production large cross-fired fur-
naces with regenerators are used for glass melt-
ing. Today, all-oxygen-fired furnaces are also
used to melt the glass. The glass tank in which
the molten glass is melted and conditioned prior
to forming is typically 9 m wide, at least 45 m
long, and usually contains more than 1200 t of
Glass 75
glass (Fig. 44). Molten glass flows from the melt-
ing tank into a bath of molten tin, 3 – 4 m wide,
50 m long, and about 6 cm deep. The tempera-
ture of the molten tin bath (650 to 1100 ◦ C) lies
in the range of the working temperature of the
glass. The glass surface flows and smooths itself
while on the float bath, taking on the excellent
surface quality of molten tin and thus requir-
ing no further polishing. The glass body is rigid
enough to be handled without damage by the
time it leaves the bath at about 600 ◦ C. Tin is
used as flotation medium because of its surface
tension (about 0.55 N/m), density (5.9 g/cm3
compared with 2.2 – 2.5 g/cm3 for glass), low
melting point (232 ◦ C), and relatively low vapor
pressure. The thickness of the float glass rib-
bon is controlled by the pull rate and top rollers,
which force the ribbon of still-molten glass to
pile up or to spread. Sometimes an inorganic
coating on the surface of the glass is directly
applied just before the ribbon exits the tin bath
section.
Figure 44. The Pilkington float glass process
a) Furnace; b) Molten tin; c) Float bath; d) Controlled nitro-
gen – hydrogen atmosphere to prevent oxidation of the tin;
e) Lehr; f) Rollers
The advantage of Pilkington float glass, apart
from the mirror quality of the glass surface, is
the high production capacity relative to other
drawing processes. The velocity of the emerg-
ing glass is about five to ten times higher than in
the Libbey – Owens process. An additional eco-
nomical advantage is that a float glass plant with
a daily production of 400 – 800 t/d can be oper-
ated by four to six persons during an 8-h shift.
6.1.8.2. Rolling
Sheet glass with figured or embossed surfaces is
formed by squeezing a stream of molten glass
between rollers that have the embossing pattern
on their surface. Wired glass is produced either
by rolling a sheet of glass, covering it with wire,
covering the wire with another sheet of glass,
76 Glass

and fusing both sheets together with the wire

between them, or by making a sandwich of two
sheets of glass with the wire between them which
is then rolled.

6.1.8.3. Overflow Process

The overflow process is used by Corning Glass

Works for specialty glasses such as ophthalmic
glass, borosilicate glass, and glass that has to be
chemically strengthened. The melt flows over
Figure 45. Rotary fiberization
two opposite sides of a trough, forming a com- a) Melting tank; b) Centrifuge with blowers; c) Binder spray;
bined sheet underneath the trough. The glass sur- d) Uncured wool; e) Binder curing oven; f) Chopper; g) Prod-
faces are untouched by a forming or handling ucts
tool until rigid, producing a surface quality com-
parable with that of glass manufactured by the
float process.

6.1.8.4. Lamination

A stressed laminated glass with all surfaces in

compression can be formed by laminating a low-
expansion glass as a skin to a high-expansion
glass core. The two glasses are fed into a laminat-
ing orifice, through which the composite sheet is
drawn. This process is used primarily to produce
food-service ware.

6.1.9. Fiberglass Forming

Four processes exist for manufacturing glass

fibers: 1) rotary fiberizing, 2) steam or air blow-
ing, 3) mechanical traction or drawing, and 4)
flame blowing. The mechanical and rotary meth-
ods are the most important.
In rotary fiberizing a stream of molten glass
is poured into a superalloy spinner rotating at
2000 – 3000 rpm. Centrifugal forces push the
Figure 46. Continuous drawing of textile glass fiber
melt up the sides of the spinner and out through a) Forehearth; b) Glass; c) Bushing; d) Size application;
the perforated band around the periphery. A e) Strand formation; f) Traversing; g) Winding
downward blast of air or hot gas stretches the
loose fibers to a diameter of 3 – 6 µm. A phe- The tanks used in mechanical drawing of
nolic binder in aqueous solution is used to bond continuous fibers contain up to 200 t of molten
the fibers together, and the fibers are collected glass. Glass furnaces with up to 100 t fiberglass
as a mat on a conveyor belt and then cured in an production per day exist. The molten glass flows
oven and cut. A typical rotary fiberization oper- from the forehearths into platinum alloy bush-
ation is shown in Figure 45. ings (Fig. 46). The bushing, provided with sev-
eral hundred nozzles, is located below a slot in
the bottom of a canal (forehearth) on top of the

spinning section where the single filaments are
spun into a single fiber (strand) by the collet.
A solution is sprayed on the filaments to estab-
lish a fixation of the filaments in the strand and
to give good adhesion properties. At the lower
end, a rotating drum (collet) is located, which
takes care of pulling and winding of the bun-
dle of glass filaments (strand) at a constant ve-
locity. Due to a meticulous system of travers-
ing the strand upon the cylinder shaped pack-
age, it is possible to unwind the strand with-
out any damage during subsequent treatment.
Strand-winding velocities vary from about 1000
to 5000 m/min. Each bushing can deliver from
several hundred up to more than 1000 glass fila-
ments to be processed as fiber strand. Diameter
control and winding techniques are similar to
those encountered in optical waveguide manu-
facture.
6.2. Annealing
Annealing of a glass product is generally nec-
essary after any forming operation. The glass is
heated uniformly to a temperature sufficiently
high to relieve any internal stress without caus-
ing excessive deformation of the object under its
own weight. The ware is subsequently cooled
slowly to prevent formation of new stresses.
Cooling may proceed as rapidly as desired once
the glass is rigid, provided that temporary stress
does not cause breakage. Glassware is normally
annealed in long, continuous ovens called lehrs,
which are usually heated electrically, but also
gas fired lehrs are applied. They are designed
with great care to ensure a uniform side-to-side
temperature, especially in the hottest zone. Bot-
tles produced at a rate of 100 t/d are annealed
in 15 – 20 min. Lehr design improvements in-
clude shortening and widening of the tempera-
ture chamber and new control techniques to en-
sure precise temperature distribution.
6.3. Secondary or Finishing Operations
6.3.1. Cutting
After emerging from the lehr, flat glass is rough-
cut by scoring with a cutting wheel or a diamond.
After inspection, the glass is cut into standard
Glass 77
market sizes. Tubing is also rough-cut after leav-
ing the conveyor, inspected for proper dimen-
sional tolerance, and then cut to the required
length. Several methods are used for this final
cutting, ranging from scoring the tube and ap-
plying mechanical stress, to local heating of the
tube with an electric wire and sudden chilling
(thermal shock).
After glass blowing, part of the glass often
has to be cut off mechanically by scoring the sur-
face and applying a stress. Then this blown ware
commonly contains broken edges. But the moil,
or waste glass, is also frequently separated from
blown ware by directing pinpoint flames onto
the glass at the cutting line and simultaneously
rotating the ware until separation of the moil and
ware edges is complete. The surface tension of
the fused glass produces a smooth, well-rounded
edge. This operation is called burn-off or flame
cutoff. Hot glass is normally trimmed by cutting
the form with a hollow plunger.
6.3.2. Grinding
The purpose of grinding is to remove the upper
layer of the glass surface. An abrasive produces
a small check or crack in the glass, the dimen-
sions of the checks depending on the grain size
of the abrasive: increasingly finer abrasive pro-
duces a relatively smooth surface. Natural abra-
sive grits (e.g., quartz, sandstone, corundum,
garnet, and diamond) are used, as well as syn-
thetic grits (e.g., silicon carbide, aluminum ox-
ide, and B2 O3 ). Water or a suitable cutting fluid
is used to speed up the process and to prevent
overheating of the glass and glazing of the abra-
sive surface in bonded grinding wheels. Con-
tinued grinding results in an interconnected net-
work of checks on the surface that break off with
the formation of new pressure points. The result
of grinding is an irregularly broken surface on
the glass. By decreasing the coarseness of the
grits in steps, the glass surface becomes more
and more polished. In using very fine polishing
techniques, the irregularities merge to a smooth
surface.
A variety of grinding machines are used for
different purposes. Grinding mills are large hor-
izontally revolving iron plates, fed with loose
abrasive grains such as silicon carbide and wa-
ter. Copper engraving wheels used to engrave
78 Glass
art glass also employ loose abrasive grains and
water. The common feature of bonded grinding
wheels, belt grinders, and diamond-impregnated
wheels is that the abrasive is embedded in the
moving part. Another method is sandblasting,
used to produce a diffuse surface.
6.3.3. Polishing
Polishing is carried out either mechanically
or chemically. Mechanical polishing requires
finely powdered abrasives such as rouge (ferric
oxide) or CeO2 . These abrasives operate on the
same principle as those in grinding. The abra-
sive is applied on a revolving buff made of felt,
leather, lead, copper, or pitch. Polishing removes
virtually no glass from the surface. The effect is
thought to arise from induced surface flow at
the molecular level, which fills local pits and re-
moves the material lying above the average sur-
face level. An optical polish produces very fine
and accurate surfaces and is an art mastered only
by specialists.
Chemical polishing includes acid polishing
and flame polishing. In acid polishing the glass
is submerged in a mixture of hydrofluoric and
concentrated sulfuric acids. The material lying
above the average surface level is preferably dis-
solved. In flame polishing a flame is directed
onto a glass surface, producing a fire polish or
fire glaze. In plasma polishing, short-term, local
high temperature (plasma temperature: 8000 –
10000 ◦ C) is used to melt the glass surface.
6.3.4. Heat Processing
In some finishing operations, reheating of glass
is required. These operations include fusion
sealing, shrinking, and tempering.
Fusion sealing is used when glass parts must
be sealed together, e.g., the spun cast television
tube (funnel) and its faceplate (panel). Fusion
sealing is often carried out electrically. The two
ends to be mated, are positioned in a lathe and
heated by gas burners until the glass becomes
sufficiently electrically conducting. At this stage
an electric arc is struck to the glass, raising the
edges of the glass pieces to the fusion tempera-
ture. The arc continues for a few seconds after
the parts are joined. The seal is worked by blow-
ing and pulling after the arc is turned off. Often,
a low melting sealing glass is used to seal two
glass parts together.
Electrostatic sealing (anodic bonding) is a
type of field-assisted glass-to-metal sealing,
which has been used successfully on steels, al-
loys, and silicon substrates. The application of
a large d.c. field to a closely-fitted glass-metal
interface allows sealing at temperatures well be-
low those required for viscous flow, wetting,
and chemical bonding. Both strong electrostatic
forces and ionic diffusion have been implicated
in the mechanism.
Shrinking is used to produce tubing with an
extremely close inside diameter tolerance, e.g.,
for fluid flowmeters. A mandrel is inserted into
the tubing, and the assembly is heated until the
glass softens. The tubing collapses onto the man-
drel after the space between the two parts is evac-
uated. Tubing of any shape (e.g., square, rectan-
gular, triangular) can be produced in this manner.
Optical glass fibers are produced from massive
cylindrical rods by heating until the glass soft-
ens and subsequently stretching the rod to the
desired fiber diameter.
Thermal tempering, or quench strengthening,
is used to strengthen glass by stressing to bring
all surfaces into compression. This finishing op-
eration is used for flat glass, piping, some cook-
ware (e.g., pots and pans), tumblers, gauge and
sight glass. The ware is heated close to the soft-
ening point at least above the strain point and
then quenched by a blast of air, a fused salt bath,
or some other means. The outer skin of the ware
solidifies whereas the inner mass remains soft,
resulting in compression of the outer skin on fur-
ther cooling. An increase in strength by a factor
of four or more can be obtained in this man-
ner, although in practice most thermal temper-
ing treatments result in a strength increase by a
factor of 2 – 3. Glass thinner than about 0.5 mm,
and glasses with very low thermal expansion co-
efficients such as fused silica, and 96 % silica
cannot be tempered.
6.3.5. Sintering
Sintering is used whenever intricate shapes such
as porous filters and tiny sealing beads are re-
quired. A variety of glass compositions from
lead glass to fused silica can be used. The glass

is finely ground, made into a paste or slurry with
a liquid, and cast or pressed to the green, inter-
mediate shape desired. After drying, the green
form is heated until the particles soften and fuse
with concomitant shrinking of the ware. Sinter-
ing usually produces a translucent glass. which
can, however, be rendered transparent with a
density similar to that of the original glass.
6.3.6. Chemical Treatment
Hydrofluoric acid is used for etching (e.g., grad-
uations on volumetric laboratory glass ware).
The item is covered with acid-resistant wax in
which the graduations are cut, and the exposed
glass is then etched by immersion in a hydroflu-
oric acid bath. Light bulbs are frosted with hy-
drofluoric acid or by injection of ammonium flu-
oride solution into the bulb.
Staining involves ion exchange between al-
kali metal atoms in the glass and copper or sil-
ver in the stain, producing a red or amber color,
respectively. Red stain is used for markings on
volumetric glassware, and silver stain for ware
with low near-UV transmittance.
Figure 47. Na+ /K+ exchange of flat glass in a KNO3 melt
at 440 ◦ C; the compressive stress at the surface reaches a
value of 430 – 480 MN/m2 after a short time.
Strengthening also involves ion exchange: the
glass is immersed in a hot salt bath, which causes
small alkali metal ions near the surface of the
ware to be replaced by the larger ions from the
bath. The surface is under compression because
of the presence of the larger ions. The degree of
compression can be as high as 700 MPa, depend-
ing on the glass composition and the strengthen-
ing cycle employed. The compressive layer can
be much thinner (100 µm) than that obtained by
Glass 79
tempering. Examples include windows of super-
sonic aircraft, glazing, and ophthalmic lenses.
Figure 47 shows the compressive stress in the
surface layers of a glass treated in a potassium
nitrate melt as a function of the duration of the
treatment.
6.3.7. Surface Coating
Vitreous enamels are applied by spraying, silk
screening, and decalomania, i.e., the transfer of
pictures from one medium to another. They are
fused to the ware at high temperature but below
the softening point of the glass itself.
Metal oxide coatings are produced either by
applying a liquid suspension of metal oxide to
the surface and then firing it or by vapor deposi-
tion of metal oxides on the glass. These coatings
are used on flat glass as a means of controlling
transmission and reflection of light, as electrical
semiconductors in tin oxide films, as resistors in
electronic circuitry, as defrosting agents and on
aircraft glazing. Metal oxide coatings (hot end
coatings) are also applied on container glass ar-
ticles to improve scratch resistance and adhesion
to polymer coatings (cold end coatings).
Metallic coatings are produced by special
coating installations that sputter metal layers
onto glass surfaces at low pressures. They are
used for thermal insulation of flat glass prod-
ucts. The coating material is bombarded with
argon (positive) ions generated in a corona dis-
charge at a high positive voltage and accelerated
in an electric field. Since the deposition source is
located at the cathode, the process is also called
cathode atomization. The atoms or molecules re-
leased from the target by the impingement of the
argon ions are deposited on the substrate. During
the sputtering process, other interactions occur
between the argon plasma particles, the target,
and the substrate, which can influence the quality
of the coating. The uniformity of the coatings is
generally good; the growth rate is typically 0.5 –
3 nm/s for d.c. sputtering. However, this rate is
too low for bulk production. The growth veloc-
ity can be increased by a factor of ten or more
by using the magnetron (microwave) sputtering
technique, in which the intensity of the argon
plasma is increased by focusing with a magnetic
field.
80 Glass
Apart from metals (Ag, Cu, Au, Ni, Cr, Ti,
etc.) also oxides, nitrides, and carbides can be
applied with the sputtering or PVD method. This
is realized by bringing reactive gas mixtures
(e.g., Ar/O2 ) into the reaction chamber (reactive
deposition/sputtering).
In physical vapor deposition (PVD) pro-
cesses the glass substrate need not be heated.
However, a chemical bond is then generally not
formed between the coating and the glass sub-
strate; there is only a weak physical adhesion.
Therefore PVD coatings on glass also are called
soft coatings. Spray or CVD coatings or mostly
hard coatings. PVD methods are used on a large
scale for the application of sunlight protection
and heat reflecting (low E) coatings on window
glass. Sun-protecting coatings partially transmit
the visible part of the spectrum (0.4 – 0.8 µm)
and reflect solar IR radiation (0.8 – 2.5 µm).
Heat-reflecting coatings must be transpar-
ent throughout the whole solar spectrum (0.4 –
2.5 µm) to obtain the heat from the solar radi-
ation, and reflective beyond 2.5 µm, where the
spectral range of the thermal radiation at room
temperature begins. In this way the heat in the
room is not lost by thermal radiation through the
windows.
Lacquers are used for decorative purposes,
for example, in Christmas ornaments and elec-
tric light bulbs.
Tin oxide and titanium oxide coatings are ap-
plied to container glass by spraying or by atmo-
spheric CVD. In the latter case, the hot bottles
pass through a reaction tunnel with an oxidiz-
ing atmosphere, in which the coating material
(e.g., SnCl4 ) is present as a vapor. In this case,
deposition of SnO2 will take place.
The CVD process is also used industrially in
combination with the float-glass process. In the
reducing atmosphere of the tin bath section, Si
layers are formed on the glass surface by treat-
ment with silane (SiH4 ). The Si coatings have
a thickness of about 30 nm and function as sun
protection mainly by reflection for wavelengths
up to 1 µm. They do not reflect heat because of
the decreasing reflection of the Si layer at higher
wavelengths ( 1 µm).
In oxidizing atmospheres SnO2 layers on the
glass surface (Pilkington) can be formed from
SnCl4 .
7. Uses
7.1. Silica and Silica-like Glass
Pure vitreous silica is the only industrially im-
portant single-component glass. The important
characteristics of this material are its extremely
low coefficient of thermal expansion, high op-
eration temperature, good chemical durability,
and excellent UV transparency (Section 2.2.1).
The principal drawback is the high production
cost resulting from the high melting temperature
(>2300 K) required to obtain transparent mate-
rial, which limits the number of economical ap-
plications. Nevertheless, several important uses
exist. A more detailed discussion of applications
of silica is given in [131].
Chemical purity, good chemical durability,
and thermal shock resistance make vitreous sil-
ica the glass of choice in chemical laborato-
ries. Thermal shock resistance is important when
making sleeves around high-temperature ther-
mocouples. Transparency to far UV radiation
and low thermal expansion are the most im-
portant properties in optical applications: e.g.,
lenses, incandescent tungsten halogen cycle
lamps, solar cell covers, high optical quality vit-
reous silica (Corning Code 1940), windows for
space vehicles, and mirror blanks. Another im-
portant application is thin-film dielectric coating
in integrated circuits. The refractory nature of
silica (SiO vapor pressure <0.87 Pa in vacuum,
and 3.9 mPa at 20.3 kPa partial oxygen pressure
and 2000 K) and its inertness make it the labo-
ratory ware of choice in the semiconductor in-
dustry.
Less critical components are made of silica-
like material ( Vycor), produced at ca. 1800 K;
the process consists of melting 65 – 86 wt %
SiO2 , 10 – 30 wt % B2 O3 , and 4 – 5 wt % Na2 O.
Glasses with these compositions exhibit phase
separation into a silica-rich and a sodium borate-
rich phase at ca. 870 K. The latter is leached
out in the presence of hot acid, resulting in a
porous “thirsty” glass with about 96 wt % SiO2
and 3 wt % B2 O3 . Heat treatment of this silica-
rich skeleton results in a dense, fully transparent
glass, used as laboratory ware.
Porous glasses have been made by (1) the
viscous sintering of powdered glass, with or
without soluble fillers, or (2) by heating and
leaching certain phase-separable borosilicate

compositions. The latter method gives mate-
rials with controlled, uniform pore diameters
of 4 – 300 nm. Applications include micro- and
ultrafiltration, chromatography packing, desic-
cants, and substrates for immobilization of en-
zymes used in biotechnology. A typical 96 %
SiO2 Vycor-type porous glass has 4 nm diame-
ter pores, a pore volume of 28 %, and a specific
surface area of 250 m2 /g.
Specialty glasses, with thermal expansion
even lower than that of fused silica, have been de-
veloped for use as astronomical mirror blanks. In
addition to silica glass, they contain TiO2 , ZrO2 ,
and B2 O3 or Al2 O3 . Inclusion of titania and zir-
conia (ZrO2 ) results in a continuous decrease in
the coefficient of thermal expansion.
7.2. Flat Glass
7.2.1. Reflective Glass
Reflective glass is covered with a metal or metal-
lic oxide coating on one surface, furnishing
high reflectivity in the desired wavelength range.
A coating that provides maximum infrared re-
flectance reduces heat losses through windows.
The coatings are produced by wet chemical, vac-
uum, or pyrolytic deposition. In wet chemical
deposition the metal is precipitated from solu-
tion onto the surface of the glass. These coatings
are fragile and must be protected after applica-
tion. Vacuum deposition involves evaporation of
the metal by electric heating in a vacuum cham-
ber. Such coatings are not as fragile as chem-
ically deposited coatings, but the glass cannot
be tempered or heat strengthened after coating.
Pyrolytic deposition involves spraying a solu-
tion containing the desired metal oxide onto the
glass, which is held near red heat. The oxide
is integrated into the surface and is extremely
durable. Glass coated in this manner can be tem-
pered and may be exposed to weather without a
protective coating.
7.2.2. Laminated Glass
Laminated glass is a sandwich consisting of a
plastic layer, usually a poly(vinyl butyral), bet-
ween two or more glass sheets. Automobile
Glass 81
windshields are made of laminated glass de-
signed to be thin enough to flex slightly, thereby
reducing the risk of injury in the event of col-
lision. The plastic inner layer may be tinted to
act as an IR filter. Laminated glass is more resis-
tant to fracture than monolithic glass, and in the
event of fracture, the plastic layer holds the glass
fragments in place and absorbs part of the im-
pact energy. Three-layer laminated glass is used
for material requiring high impact resistance.
7.2.3. Solar Glass
Solar glass is low iron oxide soda lime glass. The
IR transmittance of such glass may be as high
as 93 %. This glass is used in solar collectors
for heating water and in passive solar-heating
systems for buildings.
7.3. Laboratory Glassware
Many laboratory items (e.g., beakers, Petri
dishes, reaction flasks, volumetric equipment,
ground joints, stopcocks, fritted ware, test tubes,
and thermometers) are made from glass. The
particular composition and thermal expansion
of these glasses are given in Table 29. The cor-
responding properties of soda lime glass are in-
cluded for comparison.
Borosilicate glass has the lowest coefficient
of thermal expansion of all glass produced in
bulk. Its resistance to thermal failure is high,
and therefore, borosilicate objects can be heated
and cooled more rapidly than high-expansion
glasses. Aluminoborosilicate glass also has a
high chemical durability with an appreciably
larger expansion coefficient. Fused silica and
96 % silica glassware can be used at still higher
temperature and will, of all the glasses men-
tioned here, best withstand severe change in tem-
perature. Beakers of 96 % silica can be heated
to redness and dropped into ice water without
breaking. The four glasses listed above have few
chemical constituents, have a low alkali-metal
content, and are free from heavy-metal oxides,
a distinct advantage in chemical analysis.
82 Glass
Table 29. Characteristic thermal properties of laboratory glassware
Glass type
Borosilicate, low
expansion
Aluminoborosilicate
Soda lime
96 % Silica
Fused silica
7.4. Light-Sensitive Glass
7.4.1. Photosensitive Glass
The sensitivity of some chemicals to light has
been known since the time of Daguerre (1839).
Characteristics of such chemicals have been re-
viewed [132]. An important process for glass
applications involves cleavage of a molecule of
silver halide under the influence of light, result-
ing in its reduction to metallic silver. Photolysis
is used to produce photosensitive glass, the pro-
cess consists principally of irreversible photoin-
duced homogeneous nucleation.
Photosensitive glasses contain a small
amount of silver. Ultraviolet light or X-rays are
of sufficiently high energy to reduce the silver
ion and mobilize the homogeneously dispersed
silver atoms, causing the silver to cluster in small
particles. In Fotoform, lithium silicate is added
to photosensitive glass. Subsequent heat treat-
ment of Fotoform results in an opal glass due to
the growth of lithium meta- or disilicate crystals
that use the silver nuclei as substrates. Mask-
ing the glass before exposure produces, after
heat treatment, a pattern which duplicates that
of the mask. The exposed glass area dissolves,
because of the presence of lithium silicate, ap-
proximately 14 times faster than the unexposed
area; patterns can, therefore, be etched out, leav-
ing void areas where the glass was exposed to
radiation.
The principal use of photosensitive glasses
lies in the manufacture of intricate and precise
patterns. For example, as many as 250 000 holes,
each 0.23 mm in diameter, have been etched on
an area of 654 mm2 .
Thermal coefficient Maximum operating temperature, ◦ C
expansion, 107 K−1 Continued use Short-term use
32.5 510
55 520
80 – 90 500
8 900 1200
5.5 1000 1350 – 1450
7.4.2. Photochromic Glass
Photochromism is the change in color of a solid
upon irradiation with light of certain wave-
length. This process can be reversible or irre-
versible. Most common practical applications
use reversible photochromic materials [133].
The effect is based on the photolysis of a sil-
ver halide. In contrast to photosensitive glasses,
however, after rupture of the halogen – silver
bond, the halide ion is not sufficiently mobile
to move away from the silver atom and the bond
is reestablished during darkness. Thus the sys-
tem is excited by light and, in darkness, reverts
to its ground state.
The principal application of this effect is in
photochromic lenses, with or without a correc-
tive prescription. Corning photochromic filter
(CPF) lenses have specially formulated compo-
sitions. These lenses are fired in hydrogen, turn
yellow or red, maintain their photochromic char-
acter, and cut out blue light. They are made for
people with diseases of the cornea or retina.
7.5. Display Devices
A cathode-ray tube (CRT) consists of three parts:
a glass envelope or bulb, a phosphor screen, and
an electron gun. The bulb also consists of three
parts: the panel on which the phosphor screen
is deposited, the funnel, and the neck in which
the electron gun is sealed. These three parts are
produced separately, and two of them are sub-
sequently flame sealed with a solder glass (frit).
The panel is usually pressed, the funnel is ei-
ther pressed or centrifugally cast, and the neck
is made from glass tubing.
Cathode-ray tubes have a number of built-
in safety features. To prevent implosion, bulbs
are designed to withstand an external pressure

of at least 3 atm (303 kPa); in addition, a ten-
sion band may be placed around the periph-
ery of the panel skirt. To prevent exposure of
the viewer to X-rays, the glass composition and
wall thickness of the bulb are adjusted to max-
imize the 20.6-kV linear X-ray absorption co-
efficient of the glass; for Asahi – Corning color
TV glass, this is currently 28.5 cm−1 for panels
and 64.8 cm−1 for funnels (see also → Display
Technology, Chap. 4.).
7.6. Glass Fibers
The basic products of the glass-fiber industry are
unbonded and bonded wool, mats, staple fiber,
cut strands, textile strands, sliver (i.e., parallel,
overlapping, and untwisted bundles of noncon-
tinuous or short-length fibers), and molded prod-
ucts such as pipe insulation or ceiling tile (see
also → Fibers, 5. Synthetic Inorganic, Chap. 2.).
Glass-fiber wool insulation can reduce heat
loss to one-half to one-fifth. Typical overall co-
efficients of heat transmission, or U values, for
three wall structures are collected in Table 30.
Table 30. Typical U factors (heat conductivity) for wall structures
−2 −1
Type of construction U, W m K World production of glass is estimated at
Uninsulated
Wood frame 0.6 – 2.4
Masonry 1–4
Concrete block 1–3
∗ Based on 10-cm-thick insulation.
∗∗ Based on 7-cm-thick insulation.
7.7. Molded Optics
The impetus behind the fabrication of molded
lenses is the production of cheap optical lenses
for mass-produced cameras or optical memory
disks. The challenge is to produce a bulk optic
lens with a smooth surface and proper dimen-
sions directly by molding only, bypassing the
finishing stage. Four parameters are important
in this process: (1) the materials from which the
mold is made, (2) the variations in the mold, (3)
the molding process itself, and (4) the size of
the molded product. Glass compositions used in
this process can vary over a wide range from
Glass 83
fused silica to lead fluorophosphate. The Kodak
company is most advanced in this technology,
producing millions of aspheric lenses per year.
7.8. Glasses for Nonlinear Optical
Devices
Glasses for nonlinear optical devices represent
the frontier of research in glass chemistry and
physics. The nonlinear effect in glass consists
of a change in the refractive index of the glass
as a function of the intensity of incident light. A
necessary, but not sufficient, condition seems to
be a high-index glass [134]. This nonlinear ef-
fect is small in standard glass but, sampled over
a large volume as in optical waveguides, suffi-
ciently large to function as a switching device.
The aim is to increase photonic switching and
signal processing by producing optical transis-
tors that operate in the range of 10−12 s (ps) to
10−15 s (fs), compared with standard transistors,
which operate in the range of 10−6 – 10−9 s (µs –
ns).
8. Economic Aspects [143–147]
Insulated 80 × 106 t/a. The market shares (expressed in
0.23 – 0.35 ∗
mass %) of major applications are shown in 48.
0.4 – 0.4 ∗∗
0.32 – 0.45 ∗∗
Figure 48. Market shares of major glass applications
The most important glass producing regions
in the world are the EU with about 25.7 × 106 t
of glass production in 1995 (turnover, including
secondary glass manufacture, ca. $ 40 × 109 );
the United States with 13.5 × 106 t of glass
in 1994; and Japan and Korea with about
8 × 106 t/a of glass. Glass production is grow-
ing in China, South America, and Turkey. The
total turnover of primary glass products world-
wide is estimated at about $ 130 × 109 annually.
84 Glass
In the United States the 1994 glass production
value amounted to $ 24 × 106 .
The principal container glass producers
are: Owens Brockway (USA), Consumer
Glass (Canada), Ball-Foster (USA, owned by
Saint Gobain), St. Gobain, Gerresheim (Ger-
many), Heye Glas (Germany), BSN Embal-
lage (France), PLM (Sweden), Yamamura Glas
(Japan), Vetropack (Switzerland), Oberland
Glas (Germany, owned by St. Gobain), Sise-
Cam (Turkey), Nienburger Glass (Germany),
ACI (Australia, owned by Owens Brockway),
AVIR (Italy, owned by Owens Brockway).
Glass containers are used for food, beverages,
liquor and wine, beer, perfume, pharmaceutical,
and cosmetic products. The total container glass
production in 12 countries (Belgium, Germany,
France, Italy, The Netherlands, Ireland, Portu-
gal, Spain, Denmark, Greece, Luxemburg, UK)
of the European Union in 1994 was 16.4 × 106 t,
in the United States about 13.5 × 106 t (1994);
and in Japan 2.6 × 106 t (1990). Total an-
nual world production is about 45 – 50 × 106 t
container glass. An average 3.5 % production
growth has been accomplished since 1986 in the
EU container glass industry.
There are a very large number of domes-
tic and tableware crystal glass producers world-
wide, but the most important companies are:
Durand-Verrerie Cristallerie d’Arques (France),
Bormioli Rocco (Italy), Libbey Glass (USA),
Waterford Crystal (Ireland), Kosta Boda (Swe-
den), Sise-Cam (Turkey), Nachtmann (Ger-
many), Schott (Germany), Kedung (Indone-
sia), Crestalux (Argentina), Vitrocrisa (Mexico),
Sasaki Glass (Japan), Anchor Hocking (USA).
Annual production is estimated at 3.2 × 106 t/a.
The US turnover for tableware glass products in
1996 was $ 1.9 billion.
The major flat glass producers are: Pilking-
ton (UK), Asahi (Japan), PPG Industries (USA),
Glaverbel (Belgium), Saint Gobain (France),
Ford (USA, since 1998: Visteon), Libbey Owens
Ford (USA, owned by Pilkington), AFG (USA),
Central Glass (Japan), Nippon Sheet Glass
(Japan), Keumkang (South Korea), Hankuk
(South Korea). The companies produce mainly
float glass for automotive and architectural ap-
plications. China is an important producer of
flat glass, with about 30 – 40 operating float fur-
naces. Float glass production in the United States
in the mid-1990s was ca. 3.7 × 106 t/a. In the
EU in 1995, 5.1 × 106 t of float glass was pro-
duced. Japanese float glass production in 1990
was about 2.7 × 106 t.
Mineral wool is produced by a few large com-
panies and many small companies. The prin-
cipal mineral wool producers worldwide are:
Johns Manville (USA), Owens Corning Fiber
Glass (USA), Certain Teed (USA, affiliated to
Saint Gobain), Saint Gobain-Isover (France),
Guardian Fiberglass (USA), Knauf Fiber Glass
(USA), Rockwool (Denmark). The major mar-
kets for mineral wool are structural insulation,
industrial equipment insulation, pipe insulation,
and substitute for soils in agricultural applica-
tions.
Continuous fiberglass for textile or reinforce-
ment applications is mainly produced by PPG
FiberGlass (USA), Owens Corning Fiberglass
(USA), Vetrotex (France, owned by St. Gobain),
Johns Manville (USA), Hankuk Vetrotex (South
Korea), Asahi Fiber Glass (Japan). The EU pro-
duction of continuous fiberglass amounted to
462 000 t in 1995.
The advanced and specialty glass market in-
cludes optical waveguides for telecommunica-
tions, electronic devices such as thick-film di-
electrics, resistors, thermistors, glasses for seal-
ing ferrites in magnetic recording, electronic
displays, glass nozzles for high speed printers,
channel electron multipliers, high-performance
composites such as alumina borosilicate glass
for use in secondary structures in aircraft, medi-
cal or dental bioglasses (based on calcium phos-
phates), glass ceramics, and vitrified high-level
nuclear waste.
Among the worldwide producers of spe-
cialty glasses and TV glasses are Schott (Ger-
many), General Electric (USA), Corning (USA),
Nippon Electronic Glass (Japan), Thomson
(France), Philips Display Components (The
Netherlands), Asahi (Japan), Samsung Corn-
ing (South Korea), and Hankuk Electric Glass
(South Korea).
Glass for lighting applications, such as bulbs,
tubes, and automotive lamps, are produced by
Philips Lighting (The Netherlands), Osram Syl-
vania (Germany, USA), and General Electric
(USA).
Sodium silicates, mainly intended for further
chemical processing, are produced in Europe
and United States by companies like Henkel
(Germany), AKZO Philadelphia Quartz (The

Netherlands, USA), Rhône-Poulenc (France),
and PPG (USA).
9. References
General References
1. Ullmanns, 4th ed. 12, 317 – 366.
2. Kirk-Othmer, 11, 807 – 880.
3. P. Balta, E. Balta: Introduction to the Physical
Chemistry of the Vitreous State, Abacus Press,
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 Gluconic Acid 1

Gluconic Acid
Helmut Hustede, Joh. A. Benckiser GmbH, Ladenburg, Federal Republic of Germany
Hans-Joachim Haberstroh, Biochemie Ladenburg GmbH, Ladenburg, Federal Republic of Germany
Elisabeth Schinzig, Biochemie Ladenburg GmbH, Ladenburg, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . . . 1 4.3. Catalytic Oxidation . . . . . . . . . . . . 3

2. Physical Properties . . . . . . . . . . . . 1 4.4. Methods Involving Biotechnology . . . 4
3. Chemical Properties . . . . . . . . . . . 2 5. Uses . . . . . . . . . . . . . . . . . . . . . . 6
4. Production . . . . . . . . . . . . . . . . . . 3 6. Economic Aspects . . . . . . . . . . . . . 7
4.1. Chemical Oxidation . . . . . . . . . . . . 3 7. Physiology, Product Specifications . . 7
4.2. Electrochemical Oxidation . . . . . . . 3 8. References . . . . . . . . . . . . . . . . . . 7

1. Introduction [5]; proposals for catalytic oxidation of glucose

d-Gluconic acid [526-95-4], 1,2,3,4,5-
pentahydroxy pentane-1-carboxylic acid,
C6 H12 O7 , M r 196.16, was discovered in 1870
by Hlasiwetz and Habermann during the
oxidation of glucose with chlorine. The sub-
stance was isolated in the form of its barium
and calcium salts. Several authors subsequently
reported that gluconic acid could be obtained by
treatment of various mono-, di-, and polysac-
charides with oxidizing agents such as elemen-
tal halogen, copper(II) or hexacyanoferrate(III)
salts, or mercury(II) oxide. Depending on the
type of sugar and the oxidant employed, byprod-
ucts of the reaction include formic acid, glycolic
acid, oxalic acid, and carbon dioxide.
As early as 1880 Boutroux recognized that
gluconic acid was produced, together with acetic
acid, by the oxidative action of Acetobacter aceti
on glucose. This characteristic was also found
to be associated with numerous other bacteria
[1]. Molliard was the first to report the pres-
ence of gluconic acid in cultures of Sterigma-
tocystis nigra, now known as Aspergillus niger
[2]. The currently preferred method for prepar-
ing gluconic acid and its derivatives with the aid
of Aspergillus strains is based on the work of a
number of authors [3]. The catalytic activity of
the enzyme glucose oxidase was first described
by Müller [4].
During the 1930s anodic oxidation was sug-
gested for the preparation of calcium gluconate
with the aid of air or oxygen followed somewhat
later [6].
Sources. Gluconic acid is a naturally occur-
ring substance in humans and other organisms
(cf. Chap. 7); it is found in food products such
as wine and honey.
2. Physical Properties
Free d-gluconic acid is difficult to prepare in
crystalline form. According to Milsom and
Meers [7], crystallization of the anhydrous sub-
stance is possible below 30 ◦ C, and a monohy-
drate has been reported to crystallize at 0 – 3 ◦ C
with a characteristic crystalline structure, mp ca.
85 ◦ C [8].
Anhydrous gluconic acid is a white, odor-
less, crystalline powder, specific rotation [α]20 D
−6.7 ◦ [9], [α]25 ◦
D −5.4 [10].
Literature values for the melting point of glu-
conic acid fall in the range 120 – 131 ◦ C. The
spread in values is due to the formation of in-
tramolecular anhydrides whose presence lowers
the melting point.
Two lactones of gluconic acid are known.
These exist both in the solid state and also in
aqueous solution, where they are in equilibrium
with each other and with the free acid.
This complex equilibrium is also influenced
by the dissociation of the free acid, which has a

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 449
2 Gluconic Acid
reported [10] dissociation constant K A at 25 ◦ C
of 1.99 × 10−4 and a pK A of 3.70 (3.62 accord-
ing to [11]).
Lactone hydrolysis and formation are both
first order with respect to hydrogen ion con-
centration, with rate constants (k and b, respec-
tively) related as follows [12]:
k1,5 +b1,5 =cH+ ·5.5 × 10−2 s−1
k1,4 +b1,4 =cH+ ·4.3 × 10−4 s−1
Thus, equilibrium is established with the 1,5-
lactone roughly 100 times faster than with the
1,4-lactone. The following empirical equation
describing the kinetics of hydrolysis for the 1,5-
lactone in the pH range 0.6 – 8.2 has been re-
ported [12]:
k1,5 =cH+ ·4.7 × 10−2 +cOH− ·4 × 103
+2.5 × 10−4 s−1
This expression indicates that the OH− ion
strongly catalyzes the opening of the lactone
ring, while the H+ ion is considerably less ef-
fective. In the region of neutrality, hydrolysis is
quite slow. The rate of hydrolysis over the nar-
rower pH range 3 – 5 is given by
−dcL /dt=kcL
where cL is the concentration of the 1,5-lactone
and k= 2.3 × 10−4 s−1 . The activation energy
for the process is reported to be 62.8 kJ/mol [13].
Gluconic acid is quite soluble in water. At
20 ◦ C, commercial 50 % gluconic acid solution
has a pH of 1.82 and a density of 1.23 g/cm3 .
In this concentration region, solution density in-
creases almost linearly with increasing concen-
tration. The acid is only slightly soluble in etha-
nol and virtually insoluble in nonpolar solvents.
Storing gluconic acid over a desiccant at
room temperature or heating it above 50 ◦ C leads
to the formation of lactones. Pyrolysis occurs
above 200 ◦ C.
Gluconic acid 1,5-lactone [90-80-2] is a
white, crystalline substance with a faintly sweet
taste, mp 153 ◦ C, [α]20 ◦
D +66.2 [13]. On stand-
ing, both the pH and the specific rotation of a
lactone solution decrease as a result of hydroly-
sis, becoming constant only after equilibrium is
established. Approximately 90 g of 1,5-lactone
dissolves in 100 mL of water at 20 ◦ C; this in-
creases to about 205 g at 50 ◦ C. Only small
amounts dissolve in organic solvents. The 1,4-
lactone [1198-69-2] crystallizes as fine needles,
mp 134 – 136 ◦ C, [α]20 ◦
D +67.8 [13].
3. Chemical Properties
The action of oxidizing agents such as nitric
acid or hydrogen peroxide on either the lac-
tones or the calcium salt of gluconic acid leads
under mild conditions to mixtures of oxoglu-
conic acids, with the carbonyl groups at the
2- and the 5-positions. 2-Oxo-d-gluconic acid
[669-90-9] is the principal product of anodic ox-
idation, oxidation with sodium chlorate in acid
solution, or fermentation by species such as Ace-
tobacter suboxydans, A. xylinum, or A. glucon-
icum. Treatment with concentrated nitric acid or
with N2 O4 results in formation of glucaric acid,
HOOC(HCOH)4 COOH [87-73-0].
Hydrogenation of gluconic acid in aqueous
solution over a platinum oxide catalyst results
in a modest yield of d-glucose, whereas the 1,5-
lactone undergoes this reaction in high yield. Re-
fluxing with concentrated hydriodic acid in the
presence of red phosphorus causes reduction to
hexanoic acid [142-62-1].
The six functional groups of gluconic acid
can, in principle, react with a variety of reagents,
such as alcohols, acids, etc. Nevertheless, the re-
sulting derivatives tend to be stable only if reac-
tion is complete. Partial reaction leads to nonuni-
form mixtures that are sensitive to hydrolysis;
such reactions have little significance.

In contrast, considerable interest exists in the
ability of gluconic acid and its alkali salts to
form complexes with polyvalent cations; some
of these complexes are very stable (see Chap. 5).
Nuclear magnetic resonance spectra suggest that
complex formation involves both the carboxyl
and the hydroxyl groups.
4. Production
For commercial purposes, d-gluconic acid and
its salts are prepared exclusively by the oxida-
tion of glucose or glucose-containing raw ma-
terials. The oxidation method may be chemical,
electrolytic, catalytic, or biochemical.
4.1. Chemical Oxidation
Chemical methods have the disadvantage of lim-
ited specificity even under carefully controlled
and optimized reaction conditions, which results
in unsatisfactory yields (60 – 80 %) and undesir-
able byproducts. Isolation and purification of the
product are correspondingly difficult. Hydrogen
peroxide [14], ozone [15], and oxygen [16] have
been the oxidants of choice, presumably because
of ecological problems associated with other ox-
idizing agents and their reduction products.
4.2. Electrochemical Oxidation
Similar problems accompany electrochemical
procedures, most of which are based on the oxi-
dation potential of halogens. The usual approach
is to electrolyze a glucose solution containing
bromide (ca. 10 mol % relative to glucose) at
a current density of 1 – 20 A/dm2 . Carbonates
(preferably calcium carbonate) or hydroxides
are added to neutralize the resulting acid [17].
Electrical current yields are 80 – 86 %; the prod-
uct yield based on glucose is 80 – 97 %. The
rapid increase in the cost of electricity in recent
years has made the electrolytic process noncom-
petitive.
4.3. Catalytic Oxidation
In contrast, recent developments have led to
great improvements in the technique of oxi-
Gluconic Acid 3
dizing glucose with oxygen or air and serious
consideration has been given to adopting this
strategy on an industrial scale. Oxidation is car-
ried out, with the aid of an appropriate catalyst,
on a glucose solution whose concentration is
1 – 2 mol/L. The pH is held between 8 and 11
(preferably 9 – 10) by continuous addition of al-
kaline solution.
The catalysts originally employed were finely
divided platinum-group metals suspended on ac-
tivated charcoal, aluminum oxide, or some other
carrier [18]. The corresponding reaction mech-
anism for a Pt – C catalyst has largely been elu-
cidated [19].
The most important observations with respect
to the catalytic reaction include a rapid decrease
in activity of the catalyst from its initial levels (a
decline that cannot be completely reversed de-
spite efforts at reactivation), the need for highly
purified glucose solutions, and the formation of
various byproducts as a result of insufficient cat-
alyst specificity and the tendency of the substrate
to undergo side reactions under the prevailing
reaction conditions.
The foregoing disadvantages have been cir-
cumvented through a series of developments
with respect to the catalysts employed. Thus,
platinum-group metals have been found to be-
come more active and more selective if they are
doped with lead [20], [21], selenium [22], thal-
lium [21], or bismuth [21], [23]. The preferred
carrier is activated charcoal.
The catalyst described in [23] permits con-
version of a 2 M glucose solution to gluconic
acid with oxygen at 50 ± 1 ◦ C and pH 9.5 ± 0.2
(neutralization with 40 % sodium hydroxide so-
lution) in >99.5 % yield within 1 h. The process
is also highly selective: product purity (based
on sodium gluconate) is >99.5 %. In addition,
no special effort need be taken to purify the glu-
cose solution. Loss of catalytic activity is mini-
mal, permitting the catalyst to be recycled many
times without an intervening reactivation step.
The economic viability of the process de-
pends largely on the activity, selectivity, lifetime,
and cost of the catalyst, as well as on the mea-
sures required for product purification and the
energy demands.
Despite earlier suggestions to the contrary,
glucose cannot be oxidized photochemically to
gluconic acid [24].
4 Gluconic Acid
4.4. Methods Involving Biotechnology
The principal organisms employed today for
large-scale biological preparation of gluconic
acid are Aspergillus niger and Gluconobacter
suboxydans.
Aspergillus Niger Process. The biochem-
istry of gluconic acid formation by Aspergillus
niger is illustrated in the following diagram
[25], [26]:
where FAD and FADH2 are the oxidized and re-
duced forms, respectively, of flavine – adenine
dinucleotide. β-d-Glucose is oxidized catalyti-
cally to glucono-1,5-lactone by the enzyme glu-
cose oxidase (see also → Enzymes). Subsequent
hydrolysis of the lactone to gluconic acid is to
some extent spontaneous, but the enzyme glu-
conolactonase also plays a role.
Glucose oxidase (E.C. 1.1.3.4) [9001-37-0],
M r 186 000, contains two FAD moieties as pros-
thetic groups. These are responsible for the ab-
straction of hydrogen atoms from glucose (to
form FADH2 ), which ultimately combine with
oxygen to produce hydrogen peroxide. This is in
turn cleaved to water and oxygen by the enzyme
catalase. Both glucose oxidase and catalase are
present as endoenzymes in the fungal mycelium
[27], [28].
In addition to glucose oxidase, Aspergillus
niger may have other enzymes that also lead to
gluconic acid formation, comparable to the glu-
cose dehydrogenase and phosphomonoesterases
found in A. oryzae [29], [30].
Metabolic investigation has shown fermenta-
tion to be a three-stage process [31]: a brief lag
phase, followed by an acceleration phase dur-
ing which glucose oxidase activity rises nearly
logarithmically, and finally a stationary phase,
which is characterized by a constant rate of glu-
conic acid formation. The optimum pH for the
reaction lies near 5.6 [32].
Production Parameters. Fermentative syn-
thesis of sodium gluconate requires a steril-
ized substrate; a typical formulation is as fol-
lows: glucose 250 – 350 g/L, MgSO4 · 7H2 O
0.2 – 0.3 g/L, KH2 PO4 0.2 – 0.3 g/L, and
(NH4 )2 HPO4 or urea 0.4 – 0.5 g/L. The substrate
may be sterilized either in batches at 110 ◦ C with
a residence time of 45 min or continuously under
conditions providing several minutes exposure
to a temperature of 135 – 150 ◦ C. The sterile
medium is then transferred to the fermentation
vessel, adjusted to a pH of 4.5 – 5.0, and inocu-
lated with cultured microorganism.
The culture medium contains only about
100 g of glucose per liter, but as much as twice
the above amounts of nutrient salts, an increased
level of nitrogen compounds, and a growth-
stimulating additive consisting of 0.2 – 0.4 g of
corn steep powder (a residue obtained by evap-
orating the water in which maize has been
soaked). A lyophilized permanent culture is used
to grow the conidia. This culture is first activated
with a specific growth medium in culture tubes.
After several subcultures have been prepared,
the organism is introduced into a culture flask

containing a special medium that encourages the
formation of conidia. After an incubation period
of 5 – 10 d the conidia are harvested, either in
dry form or as an aqueous suspension, and used
to inoculate the preculture.
During the production phase, the system is
maintained at 30 – 32 ◦ C and pH 5.5 – 6.5. The
pH is controlled by continuous neutralization
with 30 – 50 % sodium hydroxide solution, the
consumption of which is an indication of reac-
tion progress. Depending on the starting con-
centration of glucose, fermentation continues
for a period of 40 –100 h. Under conditions of
maximum specific rate of product formation,
20 – 30 mmol of gluconic acid is generated per
hour for each gram of biomass (dry weight) [33],
[34].
After fermentation is complete, the microor-
ganisms are removed by filtration and washed.
The filtrate is decolorized with activated char-
coal, subjected to fine filtration, and then either
evaporated and crystallized or directly spray-
dried.
The fungal mycelium residue may be used for
the isolation of glucose oxidase or it may simply
be burnt [35].
Various attempts have been made to use
mathematical models to optimize the above pro-
cess [33], [34], [36], [37]. These efforts have
shown that both the specific rate of oxygen
uptake and the specific rate of formation of
gluconic acid increase approximately linearly
with increasing concentration of dissolved oxy-
gen or increasing oxygen partial pressure. If
the effects of the brief growth phase and re-
tentive metabolism are ignored, the produc-
tive phase follows simple Michaelis – Menten
kinetics, with K M 3.6×10−4 mol/L at 33 ◦ C
and pH 6.6 [34]. At 25 ◦ C and pH 5.6,
KM = 2.0 × 10−4 mol/L [32]. Isolated glu-
cose oxidase under these conditions has K M
4.8 × 10−4 mol/L.
To ensure economically viable yields of more
than 80 %, an adequate oxygen supply (0.1 L of
oxygen per liter of solution per minute) must be
maintained, and gas distribution within the fer-
mentor must be optimized. The oxygen partial
pressure may be increased by conducting fer-
mentation at elevated pressure or by employing
air enriched in oxygen [38].
Product concentration in the fermentation so-
lution can be increased if glucose is introduced
Gluconic Acid 5
at a higher concentration and pH control is dis-
continued near the end of the fermentation [39].
These conditions result in formation of a mix-
ture of sodium gluconate and free gluconic acid,
which has a considerably higher solubility than
the salt alone. Such a solution (e.g., Naglusol) is
suitable for commercial use in technical applica-
tions as soon as the mycelium has been removed.
Gluconobacter Suboxydans Process. The
Gluconobacter suboxydans process is rather
different, in that conversion of β-d-glucose to
glucono-1,5-lactone occurs through the action
of two glucose dehydrogenases: a particulate
quinoprotein glucose dehydrogenase and a sol-
uble NADP-dependent glucose dehydrogenase
[40], [41].
Gluconobacter suboxydans fermentation is
distinguished by a high affinity for oxygen rel-
ative to the Aspergillus process: simple aeration
suffices to ensure a high rate of glucose conver-
sion. In addition, the process displays greater
tolerance with respect to acidity, permitting the
isolation of free gluconic acid directly from the
fermentation solution [42].
Other Methods. Another approach that
leads directly to gluconic acid uses acidophilic
methylotropic bacteria (Acetobacter metha-
nolicus) under nonsterile conditions [43]. Other
procedures have been described that involve im-
mobilized enzymes, microorganisms, or both
[44–47]. To date, none of these methods is used
for commercial production of gluconate, largely
because of rapid deactivation of the enzymes or
limitations with respect to oxygen diffusion.
Downstream Processing. Ordinary com-
mercial grades of free gluconic acid may be
prepared from the corresponding sodium salt ei-
ther through cation exchange or electrodialysis.
Passage of a mixture of sodium gluconate and
free gluconic acid over a strong anion-exchange
resin results in adsorption of gluconate [48].
Glucono-1,5-lactone crystallizes from a su-
persaturated aqueous gluconic acid solution bet-
ween 36 and 57 ◦ C [49]. A two-step continu-
ous crystallization is said to result in increased
productivity per unit volume under conditions
that are favorable in terms of energy consump-
tion [50]. In the first step, a crystalline suspen-
sion (3 – 10 % crystalline material) is produced
in a supersaturated gluconic acid solution held at
6 Gluconic Acid
65 – 75 ◦ C. The second step involves controlled
cooling to 40 – 45 ◦ C, followed by a period of
crystal maturation at constant temperature. A
portion of the resulting crystalline suspension
is then recycled to the first step.
According to [51], the 1,5-lactone may also
be obtained from an aqueous gluconic acid solu-
tion by dehydration involving azeotropic distil-
lation with alcohols, followed by crystallization
from the alcohol-containing residue.
Crystallization above 70 ◦ C leads to the 1,4-
lactone.
5. Uses
The primary applications of gluconic acid fol-
low from its most important characteristic: it is a
weak acid capable of dissolving the oxides, hy-
droxides, and carbonates of polyvalent cations
without attacking metallic or nonmetallic sur-
faces. The value of this property is further en-
hanced by the fact that the acid forms water-
soluble complexes with such cations. Gluconic
acid is thus exceptionally well suited for use in
removing calcareous and rust deposits from met-
als or other surfaces, including beer and milk
scale on galvanized iron, magnesium alloys, or
stainless steel. The compound is also used in the
textile industry together with magnesium salts
as a stabilizer for peroxide bleach baths.
Because of its physiological properties, d-
gluconic acid has also been used in both the food
and beverage and the pharmaceutical industries.
Thus, low concentrations (0.02 – 0.1 %) of the
substance effect the inversion of sucrose without
causing the resulting fructose to undergo further
reaction. Trace elements are usually adminis-
tered in the form of gluconate salts because such
compounds are readily absorbed into the body
and are well tolerated. Potassium gluconate also
has certain pharmaceutical applications and may
be dispensed either in anhydrous form or as the
monohydrate.
In many applications, gluconic acid 1,5-
lactone is a convenient substitute for the free
acid. The lactone offers particular advantages in
circumstances involving acidic conditions over
a long period, e.g., in the preparation of pickled
goods and frankfurter-type sausages, or in cur-
ing fresh sausage. Another example is its use as
a leavening agent in baked goods.
The most common gluconate is sodium glu-
conate, M r 218.14, [α]25 ◦
D +12.0 [10], whose
solubility behavior is as follows:
t, ◦ C 0 20 50 80 100
c, g/100 g H2 O 43 60 85 133 160
Sodium gluconate, like the free acid, forms
complexes with metal cations. The stability of
such complexes often increases considerably
with increasing pH [13]. This salt also displays
cleansing characteristics with respect to surfaces
of widely varying type and structure.
Combinations of sodium gluconate with
sodium carbonate or sodium hydroxide solution
are useful for removing grease and corrosion
from aluminum, rust from steel, oxide coatings
from copper and copper alloys, and for etch-
ing aluminum. Strongly alkaline gluconate baths
permit the removal of zinc coatings from metal-
lic objects, castings, and scrap metal. Such baths
are characterized by a high zinc capacity and a
correspondingly long life.
Alkaline sodium gluconate solutions at
95 – 100 ◦ C are effective agents for the rapid
removal of paint and varnish, without damag-
ing underlying surfaces. Gluconate is also use-
ful in the pretreatment of certain surfaces, e.g., in
the galvanic deposition of nickel – cobalt braz-
ing surfaces onto aluminum or in the baths re-
quired for preparing smooth, shiny surface plat-
ings of nickel, tin, and zinc. In the latter appli-
cation, gluconate is increasingly used to replace
the highly toxic cyanide ion.
Mixtures of gelatin and sodium gluconate
are used as sizing agents in the paper indus-
try because they result in a product with in-
creased acid resistance. Textile manufacturers
employ gluconate (sometimes in combination
with polyphosphates) for desizing polyester or
polyamide fabrics and for finishing natural cel-
lulose fibers.
Sodium gluconate is a component of com-
mercial cleansers because of its absolute stabil-
ity to hydrolysis at high temperature and high
pH, as well as its sequestering properties with
respect to hardening agents in water. For exam-
ple, sodium gluconate is used in bottle washing
and in cleaning aluminum surfaces (e.g., build-
ing facades, aircraft, and containers).

Concrete manufacturers have found sodium
gluconate to be a highly effective agent for
retarding the curing process. Addition of
0.02 – 0.2 wt % of this substance (relative to ce-
ment) produces a very homogeneous concrete
with high resistance to water, frost, and cracking.
This material is also easily worked and shows in-
creased stability upon setting. Other advantages
accompanying the introduction of gluconate in-
clude better flow properties for the wet concrete
mixture, increased wettability with respect to
iron reinforcing structures, and maintenance of
plasticity despite reduced water content.
Relative to other organic and inorganic com-
plexing agents, gluconic acid, its lactone, and
its salts offer one major advantage: they are all
destroyed effectively and quickly by biological
wastewater treatment, whether adapted or not.
The same applies [52] to the soluble complexes
of gluconate with aluminum, copper, iron, and
zinc, although biodegradation of the chromium
gluconate complex occurs more slowly. Metal
ions released during gluconate complex degra-
dation are largely removed from the purified
wastewater, either by precipitation or by adsorp-
tion on the sludge. This circumstance reduces a
major threat that might appear to accompany the
use of gluconate as a complexing agent: mobi-
lization or remobilization of heavy metals into
surface water [53].
Destruction of heavy-metal gluconate com-
plexes in wastewater may occur not only through
biodegradation but also by simple hydroxide
precipitation [54], in which iron(III) acts as a
precipitant at a pH of 9 – 10; see also [55].
6. Economic Aspects
Annual worldwide production capacity for glu-
conic acid and its derivatives is estimated to
be 60 000 t. The bulk of production (85 %) is
in the form of sodium gluconate and other al-
kali gluconate salts. Present consumption lev-
els are, however, significantly lower, resulting
in only 60 – 70 % utilization of existing capacity.
Principal manufacturers include: Akzo-Chemie,
Amersfoort, Holland; Biochemie Ladenburg,
Ladenburg, Federal Republic of Germany;
Finnish Sugar Co. Ltd., Espoo, Finland; Fuji-
sawa Pharmaceutical Co., Osaka, Japan; Pfizer,
Gluconic Acid 7
New York, New York; Roquette Frères, Lille,
France.
7. Physiology, Product Specifications
d-Gluconic acid and its 1,5-lactone are impor-
tant intermediates in carbohydrate metabolism.
These compounds serve two important func-
tions: (1) they contribute to the synthesis
of reduced nicotinamide – adenine dinucleotide
phosphate (NADPH), which is required in the
biosynthesis of fatty acids and steroids, and (2)
they lead to the formation of ribose 5-phosphate,
which is used in nucleic acid synthesis [56].
The gluconate salts of sodium [527-07-1] cal-
cium [299-28-5], copper [13005-35-1], iron(II)
[299-29-6], and manganese [6485-39-8] are on
the list of GRAS substances [57], [58]. The glu-
conates of potassium [299-27-4], magnesium
[3632-91-5], and zinc [4468-02-4] have not been
shown to have teratogenic, mutagenic, or car-
cinogenic properties [56].
Under the food and beverage law of the
Federal Republic of Germany, d-gluconic acid
is classified as a foodstuff and not regarded
as an additive. Purity standards for gluconate
salts are prescribed in the U.S. Food Chemical
Codex (FCC III) of 1981, the U.S. Pharmacopeia
(1985), and the European Pharmacopeia. Meth-
ods of analysis can be found in [32] and [59].
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35. L. B. Lockwood in J. E. Smith, D. R. Berry
(eds.): Filamentous Fungi, vol. 1, Wiley, New
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 Glucose and Glucose-Containing Syrups
Glucose and Glucose-Containing Syrups
Fred W. Schenck, Consultant (retired), Sun City, Arizona 85373–1113, United States
1. Introduction and History . . . . . . . .
2. Properties of Glucose . . . . . . . . . . .
2.1. Structure . . . . . . . . . . . . . . . . . . .
2.2. Physical Properties . . . . . . . . . . . .
2.3. Chemical Properties . . . . . . . . . . .
3. Raw Materials . . . . . . . . . . . . . . .
4. General Principles of Starch
Hydrolysis . . . . . . . . . . . . . . . . ..
4.1. Production and Properties of
Acid Glucose Syrups . . . . . . . . . ..
4.2. Production and Properties of
Acid – Enzyme Glucose Syrups . . ..
4.3. Production and Properties of
Enzyme – Enzyme Glucose Syrups ..
5. Production of Solid Glucose . . . . ..
1. Introduction and History
The saccharides are among the most common
organic compounds found in nature and glu-
cose is by far the most abundant monosac-
charide. d-Glucose (d-glucopyranose) [50-99-
7], C6 H12 O6 , M r 180.159, is the primary
six-carbon sugar (hexose) found in the juice
of most fruits and berries. Starch (→ Starch)
and cellulose (→ Cellulose) are composed of
anhydroglucopyranose units connected through
α- and β-linkages, respectively, to form long-
chain polymers. Thus, a considerable portion of
the human diet is composed of glucose in either
the free or the polymerized state.
When α-linked polymers of glucose (starch)
are ingested, acid and enzymatic processes con-
vert these macromolecules to glucose in much
the same way that it is made commercially. The
digestive process begins in the mouth with the
action of salivary amylase. Final digestion is ac-
complished by the action of numerous other en-
zymes in the small intestine.
d-Glucose was probably known to early hu-
mans because it appears as granules in honey due
to crystallization. However, despite the abun-
dance of glucose in nature, the disaccharide su-

c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a12 457.pub2
1
1 5.1. Production of Total Sugars . . . . . .. 12
3 5.2. Production of Pure Crystalline
3 Products . . . . . . . . . . . . . . . . . . . 12
5 6. Glucose – Fructose Syrups . . . . . . . 14
5 6.1. Properties . . . . . . . . . . . . . . . . . . 14
5 6.2. Production . . . . . . . . . . . . . . . . . . 15
6.3. High-Fructose Syrups from Inulin . . 16
6 7. Analysis . . . . . . . . . . . . . . . . . . . . 17
8. Legal Aspects . . . . . . . . . . . . . . . . 18
8 9. Storage and Transportation . . . . . . 18
10. Uses . . . . . . . . . . . . . . . . . . . . . . 19
10 11. Economic Aspects . . . . . . . . . . . . . 19
12. Physiological Properties and
10 Toxicology of Glucose . . . . . . . . . .. 20
12 13. References . . . . . . . . . . . . . . . . .. 21
crose has historically been the primary sweet-
ener for humans. Sucrose is sweeter than glu-
cose, and very pure crystals can be recovered
from syrups extracted from sugar cane and sugar
beets (→ Sugar).
Most glucose, on the other hand, is bound up
as starch, requiring complicated manufacturing
processes to release its sweetness. The growth of
the glucose sweetener industry has been based
upon a classic response to market needs for im-
proved purity and functionality.
Pure glucose was first obtained from grape
juice by the German chemist A. S. Marggraf
in 1747 [1]. Proust was one of the first to pre-
cipitate α-d-glucose crystals from grape juice
in 1801 [2]. The synonym for d-glucose, grape
sugar, owes its origin to this process.
The first sweetener created from starch was
the disaccharide maltose made in China about
1000 B.C. by the enzymatic hydrolysis of rice
[3]. By 1781, it was known in Europe that
starches could be treated with acids to produce
a soluble, sweet-flavored substance [4]. This
knowledge was little more than a laboratory
curiosity until the Napoleonic Wars when the
blockade of cane sugar imports from the West
2 Glucose and Glucose-Containing Syrups
Indies provided incentive for the development
of alternative sweeteners.
In 1811, G. S. C. K irchoff, who was look-
ing for a substitute for gum arabic (used in the
manufacture of porcelain), overcooked a mix-
ture of potato starch and sulfuric acid [5]. The
sweet, syrupy substance that resulted earned him
a lifetime pension of 500 rubles per year from
the Russian Emperor.
K irchoff recognized the commercial poten-
tial of his discovery and proceeded to improve
the process. He succeeded in preparing a syrup
that crystallized partially on standing, and from
which a solid product (impure d-glucose) could
be obtained by pressing the mass in cloth sacks.
This solid material contained large quantities of
uncrystallized syrup and was quite impure. Nev-
ertheless, serious attempts were made to manu-
facture the product on a large scale. However,
the defeat of Napoleon at Waterloo made cane
sugar available once again and the venture was
abandoned.
The French chemist Saussure determined
that the acid conversion of starch was achieved
through a hydrolytic reaction that cleaved the
linkages between the anhydroglucopyranose
units in starch by adding one molecule of wa-
ter to each unit to produce the basic building
block, d-glucose. It was also recognized that
candies manufactured with glucose syrups were
not cloyingly sweet as were those made from
sucrose, thus allowing delicate flavors to reach
the palate. As a result, the “starch sugar” indus-
try developed in Europe (especially in Germany)
and in the United States [6].
Early efforts to improve the quality of “starch
sugars” were attempts to control the nonspecific
nature of the acid hydrolysis. The market needed
purer glucose, but early commercial production
(1880 – 1920) of crystalline glucose required ei-
ther repeated crystallization steps or crystalliza-
tion from nonaqueous solvents. The only solid
form of glucose available in quantity at low price
at this time was a cast product; starch was acid
converted to as high a degree as possible, evap-
orated to a thick syrup, and poured into molds
where it hardened into solid blocks. It was sub-
sequently removed from the molds, chipped into
small pieces, and sold.
In the United States in 1923, William B.
Newkirk (Corn Products Refining Company) re-
ceived a patent for developing a commercially
feasible process for the production of pure crys-
talline glucose [7]. By careful control of the con-
ditions during the crystallization step, large, eas-
ily separable crystals could be produced eco-
nomically and an industry was born.
Although glucose and glucose-containing
syrups can have functional advantages over
sucrose (higher viscosity, greater solubility,
bland flavor, etc.) in certain applications, the
unmatched sweetness of sucrose prevented
glucose-containing syrups from capturing more
than about one-fifth of the caloric sweetener
market in the United States. In many of its uses,
sucrose in aqueous solution is treated with either
acid or enzymes to produce invert syrup consist-
ing of a 50 : 50 glucose – fructose mixture (→
Fructose). Thus, in a highly converted glucose
syrup, isomerization of half of the glucose to
fructose would make starch-based syrups about
as sweet as those made from sucrose.
Glucose isomerization under alkaline condi-
tions (see Section 2.3), which increases sweet-
ness somewhat, results in a highly colored prod-
uct with off-flavor. In 1957, a xylose isomerase
enzyme was reported to convert glucose to fruc-
tose [8], and a US patent was issued to the Corn
Products Refining Company in 1960 [9]. How-
ever, no industrial activity was immediately pur-
sued in the United States, and glucose isomerase
research shifted to Japan in the 1960s [10].
Once the economical enzymatic conversion
of glucose to fructose had been demonstrated
by the Japanese, the technology moved back
to the United States. In 1965, the Clinton
Corn Processing Company (United States) and
the Japanese Agency of Industrial Science and
Technology worked together to commercialize
fructose-containing syrups made in the United
States by enzymatic isomerization of glucose.
At about the same time, the first batchwise pro-
duction began in Japan.
The degree of enzymatic isomerization of
glucose to fructose depends on a number of
operating parameters. Because higher fructose
content is desired, higher operating temperature
and/or increased reaction time is required. How-
ever, both of these process conditions reduce the
effective enzyme productivity. Although enzy-
matic isomerization of glucose to fructose in ex-
cess of 50 % db (dry basis) is possible, conver-
sion to a 42 % db fructose content was chosen as
the best balance between increased sweetness
 Glucose and Glucose-Containing Syrups
and process economics. The first commercial
shipment of 42 % fructose syrup in the United
States was made in 1968.
This new sweetener began to replace sucrose
in many liquid applications (see Table 1), but it
was not sweet enough to satisfy the demands
of the most important U.S. soft drink produc-
ers. By use of chromatographic separation tech-
niques, the 42 % fructose syrup was enriched to a
fructose content in excess of 90 % db. Blending
this enriched syrup with 42 % fructose syrup, the
sweetness level of total invert syrup was matched
at 55 % fructose content. More than 50 % fruc-
tose was required because the various glucose
polymers remaining in the syrup, due to incom-
plete starch hydrolysis have a lower sweetening
power.
The first large-scale production of 55 % fruc-
tose syrup began in 1978; by 1984, fructose
syrups derived from glucose had replaced su-
crose in nearly 100 % of the soft drinks pro-
duced in the United States, substantially reduc-
ing sucrose consumption. Today, glucose-based
sweeteners account for more than half of the to-
tal caloric sweeteners consumed in the United
States (see Fig. 1) [12].
Figure 1. Per capita US sweetener consumption by type
1965 – 2005
North America, led by the United States, is
the dominant leader in the production and con-
sumption of glucose – fructose syrups, consum-
ing 74.1 % of the world production of 11.8 × 106
t (dry basis) today, followed by Asia and Ocea-
nia at 14.8 %, with European consumers using
7.1 % and Latin America and Africa accounting
for the remaining 4 % [13]. This market dom-
inance is expected to continue for the forsee-
able future the major market growth (on a per-
centage basis) expected in Asia [14] has not oc-
curred, because genetically modified organism
3
(GMO) regulations have complicated maize pro-
curement and low sugar prices have reduced sub-
stitution incentives [15]. Consumption of glu-
cose – fructose syrups increased in the United
States, on average, by 19 % annually between
1980 and 1985 and grew much faster than pop-
ulation (4 % annually) between 1990 and 1995.
The per capita nutritive sweetener consumption
in the United States peaked about 1999; since
then, per capita consumption of glucose – fruc-
tose syrups has fallen about 1 % per year [16].
Imports of sugar-containing products may ex-
plain some of this reduction but reasons may also
include reduced economic activity and a drop
in the consumption of baked goods and cereal
products in the United States [17].
Chromatographic enrichment to > 90 %
fructose syrups has allowed the economical
production of crystalline fructose (→ Fructose)
[18]. New drying and encapsulation technol-
ogy claims to be able to produce solid glucose–
fructose syrups [19], so that they can be used in
certain dry applications as well.
2. Properties of Glucose
2.1. Structure
At the end of the 19th century, the general struc-
ture of glucose was elucidated by Emil Fischer.
He found that the six carbon atoms of the glu-
cose molecule are linked in a straight chain. At
first glucose was thought to be an open polyhy-
droxy aldehyde. However, more than 99 % of
the molecules exist as a six-membered cyclic
hemiacetal which is formed by reaction of the
aldehyde group with the hydroxy group at C 5.
As a result, glucose does not undergo the spe-
cific addition reactions (e.g., with ammonia or
sodium bisulfite) that are typical for aldehydes.
Glucose predominantly occurs in nature in
the form of the d-enantiomer which is there-
fore important commercially. d-Glucose is gen-
erally believed to exist in three crystalline forms:
anhydrous α and β-d-glucose crystals are both
orthorhombic while α-d-glucose monohydrate
crystals are monoclinic (see Fig. 2). However,
a fourth form, thought to be a hydrated form of
β-d-glucose, has been reported [22].
4 Glucose and Glucose-Containing Syrups
Table 1. Distribution by industry of crystalline glucose, glucose – fructose, and glucose-containing syrups in the United States (in 103 t,
commercial basis) [11]
Year Baking Beverage Canning Confectionery Dairy Total
Crystalline glucose
1965 177 9 23 36 5 440
1970 172 9 23 50 7 515
1975 159 18 14 63 7 515
1980 50 68 5 54 2 430
1985 57 82 2 59 1 460
1990 75 100 4 75 1 500
1997 135 118 5 90 2 560
2002 145 520
Glucose – fructose syrups
1970 18 41 9 1 5 75
1975 127 281 63 5 36 700
1980 363 1093 236 14 141 2880
1985 424 4204 286 39 211 7180
1990 440 5250 480 40 260 8270
1997 520 5270 660 45 360 10990
2002 660 5320 12060
Glucose-containing syrups
1965 209 36 104 408 159 1155
1970 222 95 100 440 213 1380
1975 313 204 172 417 277 1890
1980 195 385 127 444 240 1840
1985 142 356 141 467 274 1940
1990 180 365 165 480 275 2125
1997 200 370 170 490 350 2955
2002 180 2780

Figure 2. Crystal forms of glucose [20, 21]

A) α – Monohydrate; B) α – Anhydrous; C) β – Anhy-
drous

Conformation. In aqueous solution, d-

glucose exists as a mixture of the α and β 4 C 1
chair forms (approximately 62 % β and 38 % α
when equilibrated at 31 ◦ C [23]) that mutarotate
from one anomeric form to the other through the
open chain aldehyde form (see Fig. 3).
Chemical structure and conformation have
been confirmed with the aid of high-field nuclear Figure 3. Mutarotation and alkali isomerization of glucose
magnetic resonance spectrometry using super-
conducting magnets, advanced pulsars, and ex-
panded computer capabilities to perform one and
two-dimensional Fourier transform experiments
[24].
 Glucose and Glucose-Containing Syrups 5
Table 2. Physical properties of d-glucose
α-d-Glucose α-d-Glucose hydrate β-d-Glucose
Formula C6 H12 O6 C6 H12 O6 · H2 O C6 H12 O6
Optical rotation [α]20
D 112.2 → 52.7◦ * 112.2 → 52.7◦ * 18.7 → 52.7◦ *
Specific heat of solution (25 ◦ C), kJ/kg + 59.4 +105.1 + 26.0
* Rotation of an α/β equilibrium mixture = 52.7◦ .

2.2. Physical Properties 2.3. Chemical Properties

Some important physical properties of crys-
talline d-glucose are shown in Table 2. The large
positive heat of solution of the crystalline mono-
hydrate form imparts a unique cooling effect to
the palate when incorporated into candy and ic-
ing in the crystalline state.
Solubility is an important property of glucose
since it is crystallized commercially from aque-
ous solution and many of its commercial uses in-
volve water systems. The solubility of glucose in
water is shown in Figure 4 [25]. Below a temper-
ature of ca. 100 ◦ C, the stable, crystalline form
of d-glucose is the α-form, which crystallizes
as a monohydrate below ca. 50 ◦ C; above ca.
100 ◦ C, the β-anhydrous form is most stable.
Above a pH of 6.3, the open aldehyde form of
glucose rearranges to keto-d-fructose (Lobry de
Bruyn–van Ekenstein rearrangement → Carbo-
hydrates, see Fig. 3).
Glucose is a reducing sugar, i.e., it reacts
with oxidizing agents such as cupric hydrox-
ide. Cupric hydroxide oxidizes reducing sugars
more rapidly if the copper is kept in solution
by the formation of a complex salt with tartrate
ion (Fehling’s solution) or citrate ion (Benedict’s
solution) to form red cuprous oxide. Benedict’s
solution is the more stable and is not affected by
uric acid; hence it is preferred for detection of
glucose in urine.
The inherent reducing property of glucose
inhibits oxidative degradation in food; glucose
maintains the bright red color of tomato catsup,
red berry preserves, and red meats without the
need for artificial antioxidants.
Glucose is fermented rapidly and completely
by yeast and other organisms. The degree of fer-
mentation possible (or fermentable extract) of
glucose and glucose-bearing syrups is shown in
Table 3.

Table 3. Fermentable extract values of glucose and

glucose-containing syrups *
Substrate Fermentable extract,
wt % db
36 DE 34.8 [27]
42 DE 41.5 [27]
54 DE 53.4 [27]
62 DE 70.0 [27]
64 DE 76.0 [28]
68 DE 79.0 [28]
Glucose – fructose syrup 95.0 [27]
Crystalline glucose 100.0 [27]
* DE = dextrose equivalents; db = dry basis.
Figure 4. Phase diagram for glucose – water solutions
a) α-Glucose monohydrate and ice; b) Ice and solution;
c) Solubility of glucose in water; before mutarotation to
α-,β-equilibrium; d) Anhydrous α-glucose and solution 3. Raw Materials
(α-, β-equilibrium); e) α-Monohydrate and solution (α-,β-
equilibrium); f) α-Glucose (monohydrate and anhydrous);
g) β-Glucose and solution; h) Unsaturated solution
Starch (→ Starch) is, for all practical purposes,
the only raw material used for commercial pro-
6 Glucose and Glucose-Containing Syrups
duction of glucose-containing syrups today, al-
though efforts have been made to utilize the other
natural glucose polymer, cellulose, as well (→
Ethanol, Chap. 5.4.3).
All starches are polymers consisting of α-
linked anhydroglucopyranose units (Fig. 5 A).
Two types must be distinguished: Amylose
(Fig. 5 B) is an essentially linear molecule
in which the anhydroglucopyranose units are
linked almost exclusively via α-1,4-bonds.
Amylopectin (see Fig. 5 C) is a much larger,
highly branched molecule (the molecular mass
of amylopectin is ca. 1000 times that of amylose
[29]); α-1,4 linkages predominate but there are a
significant number of α-1,6-linkages which lead
to branching. The proportion and structure of
these fractions in starch granules vary, depend-
ing on the botanical source of the starch (Table
4). In general, amylose from grain sources has
a lower degree of polymerization (DP), ranging
from 200 to 1800, the DP of amylose from root
or tuber sources is higher (ranging from 1000 to
6200). The amylopectin fractions have a much
greater DP, averaging about 2×106 with no ma-
jor difference between starch sources.
Maize has become the leading source of
starch for conversion to sweeteners [34], al-
though starch from barley, sago, sorghum,
wheat, rice, potato, tapioca, and other starch-
bearing grains and roots serves as the raw ma-
terial for the production of glucose-containing
syrups around the world. About 70 % of the
world production of maize starch is converted
to glucose-containing sweeteners; nearly 100 %
of the glucose-based sweeteners produced in the
United States and 84 % of the production in
Japan are from maize. In Japan it is required by
law that one part potato starch is used for every
12 parts corn starch for fructose syrup produc-
tion. Although the use of wheat starch (as a co-
product of vital gluten production) is increasing
in Europe, glucose-containing sweeteners pro-
duced there also originate from maize starch. In
Australia, however, all glucose-bearing syrups
are produced from wheat starch.
In Asia, factories often use sago, tapioca, or
maize (corn) starch for glucose production, de-
pending on the availability and price of each
ingredient. The starch source and purity have
a strong influence on manufacturing require-
ments, but a variety of starches can be used suc-
cessfully.
In Thailand, for example, a syrup called “Chi-
nese Maltose” is produced from wheat and gluti-
nous rice. In Pakistan, broken rice is used to pro-
duce 42 % fructose and enzyme – enzyme glu-
cose syrups having qualities comparable to prod-
ucts made from maize starch.
4. General Principles of Starch
Hydrolysis
Hydrolysis of starch occurs when linkages bet-
ween the anhydroglucopyranose units are bro-
ken catalytically (by using either acid or enzy-
matic catalysts in the presence of heat) with the
addition of water. The formation of the monomer
(d-glucose) and of dimers having a 1,4-(maltose)
or 1,6-(isomaltose) configuration are shown in
Figure 6.
Mutarotation, (see Section 2.1), isomeriza-
tion reactions (see Section 2.3), and possible
repolymerization reactions, coupled with the
complex chemical structures of amylose and
amylopectin (which offer a number of possible
hydrolysis sites), provide the potential for the
creation of molecules having a nearly infinite
number of combinations of ketohexose units (→
Carbohydrates).
A simplified flow diagram illustrating the
process steps used to manufacture sweeteners
from starch is shown in Figure 7. Starch hydro-
lysis is catalyzed by both acids and enzymes.
Irrespective of the catalyst used, all processes
begin with a water slurry of starch granules. Af-
ter hydrolysis, insoluble protein, lipid material,
and some of the inorganic components present
initially in the starch are separated by either cen-
trifugation or filtration (or both). The presence
of free starch due to incomplete hydrolysis (de-
tected by blue or purple hue with iodine staining)
leads to difficult separation and must be avoided.
Additional impurities are removed by refin-
ing with activated carbon, decolorizing resins, or
ion-exchange resins, either singly or in combi-
nation, before evaporation to final product solids
concentration. Because color-forming bodies
are ionic in nature and are efficiently removed by
resins, the total demineralization of syrups, with
or without carbon treatment, provides a product
with improved color removal and color stability
[83]. And, the removal of ionic material, notably
chloride ions, reduces the corrosives tendencies
 Glucose and Glucose-Containing Syrups 7

Figure 5. A) Anhydroglucopyranose unit. Shown as a 5-membered pyranose ring structure with each carbon identified by
number
B) Linear molecular structure from Amylose; normally a molecule consists of 200 – 6200 units linked together with α-1,4
bonds
C) Amylopectin. Each “bead” represents an anhydroglucopyranose unit.
D) A branch point is detailed to show an α-1,6 bond

Figure 6. Hydrolysis of anhydroglucopyranose polymers

8 Glucose and Glucose-Containing Syrups
Table 4. Starch type, composition, and production [29 – 33]
Botanical Amylose Amylopectin World Principal
starch content, content, production, countries of
source wt % db * wt % db * 106 t/a production
Arrowroot 20 80 Brazil, China
Barley 19 – 23 77 – 81 Europe
Maize
Normal 26 – 28 72 – 74 27.6 United States, Japan,
Europe, former states of
USSR
Waxy 0–2 98 – 100 United States
High-amylose 55 – 85 15 – 45 United States, Australia
Potato 20 – 24 76 – 80 2.7 The Netherlands, Japan,
Poland, former states of USSR
Rice 14 – 26 74 – 86 Asia, South America
Sago 27 73 < 0.1 Indonesia, South America
Sorghum 22 – 27 73 – 78 Asia, United States
Tapioca 17 – 22 78 – 83 3.65 Thailand, Brazil
Wheat 19 – 27 73 – 81 2.92 Australia, Europe,
United States
* db = dry basis

of syrups allowing the use of less expensive ma-
terials of construction in process equipment lo-
cated after ion exchange.
Glucose-containing syrups are generally cat-
egorized by their degree of conversion as mea-
sured by the amount of reducing sugars present.
Although it is becoming more common for cus-
tomers to specify a range of saccharide distri-
bution to obtain desired functionality, glucose
syrups can be divided into groups on the basis
of their dextrose equivalent (DE) as shown in
Table 5.
Table 5. Classification of glucose-containing syrups according to
dextrose equivalents (DE)
Degree of hydrolysis Accepted terminology
< 20 DE maltodextrins
20 – 38 DE type I syrup
38 – 58 DE type II syrup
58 – 73 DE type III syrup
≥ 73 DE type IV syrup
Most glucose-bearing syrups are sold in liq-
uid form usually containing between 70 and
85 % dry substance, but they can also be dried
to form granular, semicrystalline, or amorphous
products. These “solid syrups” range in degree
of conversion from low-DE maltodextrins to
highly converted (> 96 % DE) “total sugars”
[84].
4.1. Production and Properties of Acid
Glucose Syrups
In the acid conversion process, a starch slurry
usually having a dry substance content between
30 and 40 wt % is acidified to pH 2 or lower and
subjected to a combination of time, temperature,
and pressure to effect hydrolysis. Higher temper-
ature, permitted by operation under pressure, re-
duces the reaction time considerably. Kirchoff’s
conversion at atmospheric pressure, for exam-
ple, lasted 36 h, early starch converters that were
limited to pressures of 35 kPa took 6 h to com-
plete the reaction. At 415 – 620 kPa and up to
160 ◦ C, modern converters accomplish the con-
version within minutes. Acid conversion can be
accomplished by using either batch or continu-
ous equipment although continuous conversion
is used almost universally today.
When the desired degree of conversion is
achieved, temperature and pressure are reduced
and the reaction is stopped by addition of a neu-
tralizing agent (usually sodium carbonate), rais-
ing the pH to 4 – 5.5. Insoluble compounds are
then removed, and the syrup is refined and evap-
orated to the desired final concentration.
While acid conversion is a random-action
mechanism, it results in remarkably repro-
ducible saccharide composition for any given
degree of hydrolysis. Typical compositions of
acid glucose syrups are shown in Table 6. This
reproducible composition is actually a limitation
of the acid process because the manufacturer
 Glucose and Glucose-Containing Syrups 9

Figure 7. Simplified process flow for the production of sweeteners from starch
* HFS = High-fructose syrup
Table 6. Saccharide composition of acid-hydrolyzed glucose syrups
Degree of Dextrose equivalent (DE) of glucose syrup
polymerization 27 – 30 34 – 36 42 – 43 55
DP 1 (glucose) 9 – 10 13 – 14 19 – 20 31
DP 2 (maltose) 8–9 11 – 12 14 18
DP 3 (maltotriose) 9 – 10 10 12 12 – 13
DP 4 (maltotetrose) 7–8 8–9 9 – 10 10
DP 5 (maltopentose) 7 8 8 7
DP 6 (maltohexose) 6 6–7 7 5
DP 7 (higher sugars) 50 – 54 40 – 42 29 – 31 16 – 17

cannot influence the saccharide distribution for
a given degree of conversion, which is important
in some applications of glucose syrups.
Additionally, acid syrups having a DE value
below ca. 30 will tend to cloud upon stand-
ing due to precipitation (retrogradation) of the
longest chain linear polymers. Also, although
acid hydrolysis to DE values in the high 80s
is possible, the extreme conditions required to
produce DE values greater than ca. 55 pro-
10 Glucose and Glucose-Containing Syrups
mote the formation of excessive amounts of
glucose degradation products (e.g., 5-hydroxy-
methylfurfural see Section 2.3) which are diffi-
cult to remove during refining. These color pre-
cursors cause the product to yellow eventually.
The most common acid glucose product has a
DE value of about 40 – 45 % because of these
upper and lower conversion limitations.
The limitations at both the low and the high
ends of the conversion spectrum, coupled with
the inflexible saccharide distribution resulting
from acid hydrolysis, led manufacturers to in-
vestigate enzymatic hydrolysis as a means of
making improved glucose-containing syrups.
4.2. Production and Properties of Acid –
Enzyme Glucose Syrups
Coupling a secondary enzymatic hydrolysis to
a preliminary acid cleavage allows expansion of
the range of DE values both up and down. It also
permits control over the saccharide distribution
by enzyme selection.
After acid hydrolysis, the temperature is low-
ered and the pH is raised to levels compatible
with the enzyme to be used; a pH between 4
and 6, and a temperature in the range of 60 –
70 ◦ C are usually employed. Additionally, the
degree of acid hydrolysis is usually (but not al-
ways) lower when making acid-enzyme syrups
(see also → Enzymes, Chap. 5.1.3.2).
If the goal is a high glucose content, con-
trol of the acid hydrolysis step to produce a
DE of 10 – 20 is important. Higher DE levels
result in reduced glucose yield during subse-
quent enzymatic hydrolysis due to the presence
of acid-polymerization products that resist enzy-
matic conversion; conversely, starch retrograda-
tion can occur with a DE less than 10, resulting
in problems during clarification.
If maximum glucose content is not the aim, a
higher DE value is usually chosen and the syrup
can be clarified immediately after acid hydroly-
sis or the insoluble substances can be allowed to
remain during enzymatic conversion.
If the insoluble compounds are removed, the
acid hydrolysate can be enzymatically converted
continuously, by using immobilized enzymes;
otherwise, a batch treatment (with single use of
the enzymes) must be employed.
When the desired level of enzymatic conver-
sion is achieved by batch conversion, residual
enzymes are deactivated with heat or pH adjust-
ment, or are removed by refining. With immobi-
lized enzyme treatment, the degree of conversion
is controlled by the flow rate through a bed of
insoluble enzymes; because the enzymes remain
in the converter, their removal from the syrup is
unnecessary. Refining and evaporation follow as
in acid glucose syrup manufacture.
Bacterial α-amylases (E.C. 3.2.1.1) [9000-
90-2] cleave α-1,4-linkages in a random fash-
ion whereas β-amylases (E.C. 3.2.1.2) [9000-
91-3] (and to a lesser degree, fungal α-
amylases) mainly produce maltose, again only
cleaving α-1,4-linkages. Glucoamylase (E.C.
3.2.1.3) [9032-08-0], on the other hand, splits
off one glucose molecule at a time from the
non-reducing end of the polymer by hydrolyz-
ing α-1,4-linkages; glucoamylase also has the
capability of splitting α-1,6 linkages but at a
much slower rate. Pullulanase (E.C. 3.2.1.41)
[9075-68-7] can split α-1,6-linkages, and addi-
tion of this enzyme in combination with another
enzyme(s) increases the capability of tailoring
saccharide distributions [30].
At first, enzyme conversion was used to ex-
tend the degree of conversion upward, primarily
to maximize glucose production for the manu-
facture of crystalline glucose as well as for the
production of sweeter, less viscous glucose-con-
taining syrups. However, it also enabled selec-
tive production of either more maltose or more
glucose, depending upon the enzyme chosen.
This is illustrated by the compositional data
shown in Table 7.
4.3. Production and Properties of
Enzyme – Enzyme Glucose Syrups
The development of α-amylase from bacterial
sources capable of withstanding the high tem-
perature needed to gelatinize starch completely
allowed the development of totally enzymatic
processes that further expanded control of sac-
charide range and distribution. A total enzymatic
conversion process eliminates the need for pre-
liminary acid hydrolysis.
Thermostable α-amylases are added to a
starch slurry (containing calcium as an enzyme
stabilizer) that has been adjusted to a pH of

Table 7. Saccharide composition of various acid – enzyme glucose syrups
High maltose
DE DE 42 – 43
DP1 (glucose) 6–8%
DP2 (maltose) 40 – 45 %
DP3 (maltotriose) 12 – 15 %
DP4 (maltotetrose) 3–7%
DP5 (maltopentose) 2%
DP6 (maltohexose) 2%
DP7+ (higher polymers) 26 – 30 %
DP = Degree of polymerization.
6 – 6.5. A pH lower than 6.3 is preferable to
prevent the formation of maltulose (4–O-α-d-
glucopyranosyl-d-fructose) [35]. Maltulose can-
not be converted enzymatically to glucose and
its formation reduces glucose yield.
The recent introduction of a novel α-amylase
capable of liquefying starch at pH 4.5 without
the need for calcium ion addition has the po-
tential to reduce chemical and refining costs as
well as possibly eliminate the formation of mal-
tulose. This enzyme’s action pattern reportedly
can increase the production of saccharides with
low DP (1 – 4) while practically eliminating the
higher saccharides (DP 8+). This characteristic
allows higher solids levels during liquefaction
[36]. While presently employed for the manu-
facture of ethanol from starch and whole grains,
the application in the manufacture of starch sug-
ars holds interest.
The slurry is heated, usually by direct steam
injection, to ca. 103 – 107 ◦ C and held for 5 –
10 min to liquefy the starch completely. A sub-
sequent holding period of 1 – 2 h at about 95 ◦ C
allows continued enzymatic activity to raise the
DE to a value between 10 and 15. The temper-
ature and pH are then adjusted to levels com-
patible with the enzyme used for the secondary
conversion. From this point, the process is sim-
ilar to the acid – enzyme process.
On the high end of the glucose conversion
scale, a totally enzymatic conversion greatly in-
creases the yield of glucose while decreasing
the refining requirements. The composition of
highly converted syrups produced by acid, acid
– enzyme, and totally enzymatic hydrolysis with
respect to glucose concentration and impurity
content is shown in Table 8.
Maximum glucose content during glucoamy-
lase saccharification is also determined by solids
content in the slurry; at 30 wt %, a glucose level
Glucose and Glucose-Containing Syrups 11
High glucose
DE 48 – 50 DE 60 – 63 DE 70 DE 95
9 – 10 % 31 – 36 % 43 – 47 % 92 %
50 – 53 % 31 – 36 % 27 – 30 % 4%
14 – 15 % 10 – 13 % 5–7% 1%
1–2% (DP4+ = 20 – 23 %) 4–5% 1%
2% 3–4% (DP5+ = 2 %)
2% 2–3%
18 – 20 % 9 – 10 %
of 96 wt % db is usually achieved. Decreasing
the solids content to 10 – 12 wt % allows glu-
cose levels of 98 – 99 wt % db to be reached.
This higher glucose yield is produced at the
expense of increased evaporation cost and risk
of microbial contamination, and is seldom used
commercially because chromatographic separa-
tion technology has become available and allows
the increase of the glucose content of syrups to
be > 99 wt % db. Nanofiltration has also been
used to enrich glucose content [37].
Total enzymatic conversion also affects the
characteristics (via saccharide distribution) of
less highly converted glucose-bearing syrups, as
shown in Table 9. Syrup viscosity is an impor-
tant property that can be affected by shifting sac-
charide distribution.
The viscosity is increased mainly by the
longer chain polysaccharides. Thus, at a con-
stant DE value, solids content, and temperature,
an acid-hydrolyzed syrup would have the high-
est viscosity, an acid – enzyme syrup would be
intermediate, and an enzyme – enzyme syrup
would have the lowest viscosity. Viscosity af-
fects the handling and storage temperature as
well as the application properties. Many de-
sirable results occur from lowering the viscos-
ity, including improved flavor release in sweets,
lowering of boiling temperature in candy manu-
facture, faster operation of candy production
lines, and better “set” in jellies and jams.
Enzymatic conversion also allows the pro-
duction of syrups with reduced glucose content.
In the presence of protein, glucose undergoes
non-enzymatic browning due to the Maillard re-
action more readily than polymers of glucose.
Syrups with higher concentrations of glucose
polymers are more color stable.
12 Glucose and Glucose-Containing Syrups
Table 8. Effect of conversion method on composition of filtered unrefined highly converted glucose-containing syrup
Glucose content, %
Ash content, %
HMF content, ppm *
Color (relative)
* HMF = 5-hydroxymethylfurfural.
Table 9. Saccharide distribution of 42 DE syrups produced by different conversion methods
Degree of Conversion method
polymerization Acid
DP 1 19
DP 2 14
DP 3 12
DP 4 10
DP 5 8 2
DP 6 7 2
DP 7+ 30
5. Production of Solid Glucose
Whereas most glucose is sold as glucose-con-
taining syrups, a portion is sold as granular free-
flowing solids. In this form it can be incorporated
into dry mix products and shipped without the
added cost of transporting water. Bagged prod-
uct accommodates smaller-scale users. Solid
products include total sugars and pure crystalline
forms of glucose (dextrose). Total sugars are so-
lidified hydrolysates that can either be in glassy
(amorphous) or crystalline states. Pure glucose
crystals are grown from aqueous solution to form
a slurry of pure crystals in mother liquor (masse-
cuite), the crystals are separated from the mother
liquor by centrifugation and dried in hot air dry-
ers.
5.1. Production of Total Sugars
When the entire starch hydrolysate is solidified,
it is called a total sugar. A variety of processes
have been developed to produce total sugars
[84]. Dry maltodextrins have a DE of less than
20 while corn syrup solids have higher DE val-
ues, commonly between 24 and 48. Highly con-
verted total sugars usually contain between 95
and 99 % db glucose although processes have
been patented for the production of fructose-
bearing total sugars and solid starch sugars that
incorporate other ingredients such as intense
sweeteners.
Conversion method
Acid Acid – enzyme Enzyme – enzyme
86 93 97
1.6 0.4 0.1
3000 80 30
10 0.3 0.2
Acid – enzyme Enzyme – enzyme
6 2.5
45 56.0
12 16.0
3 0.7
0.4
0.7
30 23.7
About 40 % of the crystalline glucose sold
in Japan is a solidified hydrolysate (total sugar
form) of monohydrate glucose distantly related
to the cast product produced early this century
(but of much higher purity due to enzymatic
starch hydrolysis, modern refining methods, and
evaporation under high vacuum).
More than half of the crystalline glucose sold
in Korea is also a monohydrate total sugar that
is used as a carrier in many dry foods. These
total sugars are produced by using a modern,
continuous solidification process that employs
spray drying of a partially crystallized, refined
hydrolysate [38, 39].
However, with the exception of a relatively
small amount of spray-dried hydrolysate prod-
ucts (a monohydrate product with the trade
name Cantab produced by Penford Products
Products Co., United States and an anhydrous
product manufactured by Cargill, United King-
dom/United States), total sugars have not been
the large market successes in the West that they
have in the Orient; in Europe and the Americas,
pure glucose crystals (in either the monohydrate
or the anhydrous form) are the more universally
accepted product.
5.2. Production of Pure Crystalline
Products
Initially, crystalline glucose was produced from
acid-converted starch hydrolysates. Because of
degradation products formed during conversion,
 Glucose and Glucose-Containing Syrups
the maximum glucose content achievable in the
hydrolysate was limited to about 88 % db. By
1938, enzymatic conversion processes were be-
ing developed that provided much purer sources
from which crystalline glucose could be manu-
factured.
Either continuous or batch crystallization can
be used to produce the desired crystals. In con-
tinuous crystallization, supply liquor is either
mixed with recycled seed crystals or new crys-
tals are formed by spontaneous nucleation. In
batch crystallization, a portion (usually 15 –
30 %) of the finished batch is retained in the crys-
tallizer and mixed with the supply liquor.
Supersaturation to promote crystal growth
can be achieved by either cooling or evapora-
tion [40, 41]. When continuous crystallization
is employed for the production of monohydrate
dextrose crystals that form below 50 ◦ C, great
care must be taken to prevent microorganisms,
primarily yeast, from acting on the glucose solu-
tion. Yeast fermentation is only a problem at the
lower temperature and solids levels, that occur
at high crystal content at the final crystallization
conditions.
When producing glucose monohydrate, batch
crystallization has the advantage that the oper-
ating conditions at the beginning of the cycle
(highest temperatures and solids content) are
hostile to yeast. Thus, when hot supply liquor
is mixed with a portion of the previous batch,
any yeasts that might be present are killed.
Because a conventional batch crystallizer
process retains a portion of the finished prod-
uct to be mixed with supply liquor for the next
batch, a more efficient process for the produc-
tion of glucose monohydrate has been proposed
[42]. By continuously producing a lean phase
massecuite in a continuous crystallizer, that is
operated at temperature and solids level hos-
tile to yeast, and then supplying this material
to a batch crystallizer to produce a high-crystal-
content massecuite suitable for centrifuging, the
full operating volume of the batch crystallizer
is used for production; the batch crystallizer is
completely emptied at the end of the crystalliza-
tion cycle, and the processing time devoted to
seed mixing is eliminated.
Since anhydrous glucose crystals form above
50 ◦ C, yeast fermentation is not an issue and ei-
ther batch or continuous crystallization can be
used.
13
Production of Glucose Monohydrate Crys-
tals. The α-d-glucose monohydrate crystals,
usually produced by batch crystallization, have
the largest share of the world market. Starting
material for the manufacture of glucose crys-
tals is a syrup with a glucose content of 95 –
96 wt % db produced by enzymatic hydrolysis
of starch to the highest practical degree. This
syrup is produced and refined by using the pro-
cess described previously for the production of
enzyme – enzyme glucose syrups.
In a typical batch crystallization process, the
syrup is evaporated to a solids content of 74
– 79 wt %. Higher solids content results in in-
creased crystallizer productivity [43]. The sup-
ply is cooled to about 46 – 50 ◦ C, and mixed
with seed crystals (left behind from the previous
batch) in crystallizers (see Fig. 8). As mentioned
previously, an alternative process having greater
productivity would utilize continuous crystal-
lization to produce a lean massecuite that would
be supplied to the batch crystallizer, thus allow-
ing complete emptying of the batch unit at the
end of the cycle. Alternatively, continuous crys-
tallization could be used entirely.
Figure 8. Batch monohydrate glucose crystallizer
A) Cutaway view showing internals a) Motor and Speed
reducer which drives coil; b) Cooling water connections;
c) Rotating coil – agitator; d) External vessel shell
B) External side view a) Supply liquor inlet; b) Inspection
hatch; c) Bearing; d) Cooling water connections; e) Support
saddle; f) Massecuite discharge valve
The resulting mixture is cooled slowly, usu-
ally by indirect heat transfer to a final tempera-
ture between 20 and 40 ◦ C over 2 – 5 d during
which about 60 % of the glucose is crystallized
in the α-monohydrate form, yielding a viscous
14 Glucose and Glucose-Containing Syrups
magma of crystals and mother liquor. Exact val-
ues of the solids concentration, the initial and
final temperatures and the rate of cooling de-
pend on the glucose content of the crystallizer
supply [44 – 46].
The resulting magma is routed to perforated
screen centrifuges (usually batch machines) to
separate most of the mother liquor from the crys-
tals; most of the remaining mother liquor is then
removed by washing the crystals with a spray of
water.
The crystals are spun as dry as possible (about
14 wt % moisture content) and then transferred
to continuous rotary dryers (→ Drying of Solid
Materials) where they are dried in a stream of
warm, filtered air to 8.5 – 9.0 wt % moisture
content, slightly below the theoretical moisture
content of the monohydrate (9.08 wt %).
Because crystallization of glucose monohy-
drate occurs satisfactorily despite the presence
of large quantities of impurities [4, 47], the
mother liquor can be reconcentrated and a sec-
ond crop of crystals can be recovered. The pres-
ence of impurities alters the crystal size and
shape; purer liquors produce longer, narrower
crystals than those produced from less pure so-
lutions [48].
Otherwise, a portion of the mother liquor can
be recycled and combined with the incoming
hydrolysate as supply to a single crystalliza-
tion step. Either process increases the yield of
glucose crystals from a given amount of hy-
drolysate. Recovery of as much as 87.5 % of
the glucose from the incoming hydrolysate as
monohydrate crystals has been reported [49]. By
reconverting the mother liquor, yields approach-
ing 100 % have been reported [85].
Production of Anhydrous Crystalline Glu-
cose. Anhydrous crystalline glucose is produced
in evaporative crystallizers operated in either a
batch or a continuous mode. Anhydrous α-d-
glucose is usually produced in batch vacuum pan
evaporative crystallizers operated at 60 – 65 ◦ C.
The crystallization cycles are much shorter than
those needed for monohydrate production, usu-
ally only 6 – 8 h [4]. The crystals are separated
from the mother liquor, washed, and dried in a
manner similar to monohydrate crystals, but the
final product moisture is less than 0.1 wt %.
Production of anhydrous glucose crystals is
more demanding than that of their monohydrate
relatives and they can only be successfully crys-
tallized from relatively pure solutions [4]. The
purest grades (U.S.P.) are produced from very
pure glucose syrups made by dissolving mono-
hydrate glucose crystals in water.
Anhydrous β-d-glucose can be produced by
operating the crystallization step slightly above
100 ◦ C [4]. Another commercial method of
preparing a crystalline glucose total sugar rich
in the β-anomer consists of spraying a hot, con-
centrated glucose syrup onto a moving bed of
previously made product at high temperatures
(85 – 105 ◦ C) in a rotary dryer to yield a granu-
lar, pearl-shaped crystal [50].
The β-anhydrous glucose is much more sol-
uble than the α-form (72 wt % vs. 30 wt % at
25 ◦ C, the solubility of the equilibrium α-β-
mixture is 51 wt % at 25 ◦ C).
6. Glucose – Fructose Syrups
6.1. Properties
Isomerization of glucose to fructose signifi-
cantly increases the sweetness of starch-based
sweeteners. This single property propelled the
market share of starch sweeteners from 20 to
over 50 % in the United States. More than half
of the starch-based sweeteners sold in Japan
and about two-thirds of those sold in the United
States are 42 and 55 % fructose syrups.
Sweetening Power. Sweetening power can-
not be measured quantitatively in absolute
terms but can be determined subjectively by
using trained taste panels. Many factors in-
cluding stereochemical configuration influence
the perception of sweetness: α-glucose is def-
initely sweeter than the β-form [51]. Stere-
ochemistry can explain the wide variation in
reported sweetness of fructose, whose crys-
talline form β-d-fructopyranose undergoes rapid
tautomerization in solution to five forms: α
and β-d-fructopyranose as well as α and
β-d-fructofuranose and open chained keto-d-
fructose. Thus, although crystalline fructose is
reportedly 1.8 times as sweet as sucrose, solu-
tions of fructose are much less sweet than crys-
talline fructose because of the tautomeric distri-
bution in water [52].
 Glucose and Glucose-Containing Syrups
Figure 9. The relative sweetness of glucose-containing and fructose – glucose syrups vs. composition
All data at about 10 wt % solids water solutions, except [54]
[55]; [56]; ◦ [51];  [54];  [53];  [57]; + [58];  [59];
 [60]; ♦ [61];
Concentration [51], temperature, and pH [53]
affect the perception of sweetness too. To elim-
inate the possibility of enzymatic hydrolysis in
the taster’s mouth, rapid and consistent evalu-
ation procedures are required, especially when
tasting low-DE syrups.
In general terms, however, as the glucose
content of glucose-containing syrups increases,
sweetness increases; as glucose is isomerized to
fructose, sweetness increases further. The sweet-
ness of glucose-containing syrups, relative to su-
crose, in solutions of about 10 wt % solids con-
centration is shown in Figure 9.
Most glucose–fructose syrups are usually
produced from enzymatically converted high
glucose (95 – 96 % db) hydrolysates which are
the fructose–glucose syrups shown in Figure
9. However, lower DE syrups that have been
isomerized slightly to 10 wt % fructose content
to increase sweetness are sold in the European
Union. Syrups isomerized to this low level do
not violate fructose production quotas that have
been established to protect domestic sucrose
production.
Chemical Properties. Fructose reacts with
amino groups (Maillard reaction) much more
readily than glucose does (→ Fructose) [62].
Therefore, glucose – fructose syrups must be re-
15
fined to a greater degree and are inherently less
stable. Fortunately the higher water solubility of
fructose (→ Fructose) allows lower storage tem-
peratures without crystallization (see Chap. 9).
6.2. Production
The clarified, refined, and ion-exchanged high-
glucose-content syrup is evaporated to a 40 – 50
wt % solids level. Magnesium(II) ions (usually
as MgSO4 ) are added as a cofactor to activate
and stabilize the isomerase enzyme, as well as
to overcome the inhibitory effect of residual cal-
cium not removed by ion exchange.
This feedstock is then passed through reac-
tors containing immobilized glucose isomerase
(E.C. 5.3.1.18). Process conditions vary de-
pending upon the supplier of the enzyme but
most systems operate at 55 – 65 ◦ C and with pH
of 7.5 – 8.5. The flow rate is adjusted to yield a
product having a minimum of 42 % of the dry
substance converted to fructose.
Enzymatic activity decreases during the ef-
fective life of the reactors due to thermal inac-
tivation and the presence of trace impurities in
the feed liquor. Fructose content is maintained
at the desired 42 % level by reducing the flow
rate through the columns. The effective life of
16 Glucose and Glucose-Containing Syrups

a reactor is several months; during this period, supply a crystallization process to produce fruc-
the nominal retention time in the reactor may tose crystals.
increase typically from 0.5 to as much as 4 h. In 1987 more than 80 commercial factories
Immediately after isomerization, the pH is on almost every continent were reported to pro-
lowered to 4 – 5, the syrup is refined and evap- duce more than 6.6×106 t (dry basis) per year
orated to the final concentration. of glucose–fructose syrups [65]. Worldwide pro-
duction increased to 10.1×106 t (dry basis) per
Chromatographic Enrichment. Although year in 1995 and is estimated to have grown to
42 % db fructose syrups are nearly as sweet as nearly 12.5×106 t (dry basis) in 2002 before
sucrose, the fructose content had to be increased dropping to 11.8× 106 t (dry basis) per year
to 55 % db to provide the exact sweetness match in 2005 [14]. The phenomenal growth of glu-
demanded by the soft-drink market. This is cose – fructose syrup (called high fructose corn
accomplished by employing chromatographic syrup or HFCS in the United States) production
separation techniques to separate 42 % fruc- is shown in Figure 10.
tose syrups into fructose-enriched and glucose-
enriched streams.
Separation is accomplished by passing the
42 % fructose syrup through an adsorbent resin
containing calcium ions. Fructose is bound to
the adsorbent to a greater extent than glucose
(and polymers of glucose). Elution with wa-
ter produces a discharge stream initially rich in
the loosely bound glucose and glucose polymer
fraction, followed by a fraction rich in the more
tightly bound fructose. A continuous (simulated
moving bed) process is used commercially, in
which 42 % fructose supply liquor and elution
water enter the columns at different points, while
glucose-rich and fructose-rich product streams
are withdrawn at others. The points of addition
and withdrawal are moved along the bed period-
ically to correspond to changes in composition
within the column [63, 64].
Typical operation uses 50 wt % solids feed-
stock (42 % fructose). The separation produces
a glucose- and glucose-polymer-rich byproduct
stream that is recycled either to the isomerization
step (to convert additional glucose to fructose)
or back to the hydrolysis step (to convert the
glucose polymers to glucose). A fructose-rich
Figure 10. Growth of glucose – fructose syrup production,
stream containing 80 – 95 % db fructose is the 1968 – 2005
primary product (the composition depends on
the equipment and operating conditions). This
fructose-rich stream is blended with 42 % fruc-
tose syrup to produce a 55 % fructose syrup that 6.3. High-Fructose Syrups from Inulin
is refined and evaporated to the final concentra-
tion. Inulin is a naturally occurring polymer of fruc-
The fructose-rich stream can also be refined tose which replaces starch as the food reserve
and evaporated to about 80 wt % solids for cus- in many plants of the family Compositae (e.g.,
tomers requiring a very high fructose-content Jerusalem artichoke, chicory, salsify, cardoon
product. At the highest fructose levels, it can elecampane, burdock, dahlia, and ti plants).
 Glucose and Glucose-Containing Syrups 17

Figure 11. Part of an inulin chain

The mature inulin molecule has an M r to make a range of nondigestible oligofructose

of 3000 – 5000 and consists of 17 – 30 anhy- ingredients that are finding use as fat mimetics.
drofructose units and a terminal glucose unit Only the European Union is a substantial pro-
(see Fig. 11). The chain length varies during the ducer of fructose-containing inulin syrup that
growing season, and consequently, the glucose originally was not limited by production con-
– fructose ratio is not constant [66]. trols as was glucose-derived fructose syrups. In-
A process for the production of high-purity ulin syrups have now been brought under control
fructose syrup from inulin-containing roots has by the EU.
been described [67]. The pH of extracts is raised
to > 11 using lime, to precipitate impurities. Un-
der these conditions, inulin is not precipitated by 7. Analysis
high levels of calcium (as is fructose) and can be
Solids concentration of glucose-containing
recovered by filtration [68].
syrups is usually measured by refractive in-
The lack of commercial interest in high-
dex or density. This measurement can be re-
fructose syrup production from inulin is prob-
lated to dry substance or the more traditional
ably due to the high quality of fructose syrups
Baumé or specific gravity values by using es-
produced by isomerization of glucose followed
tablished mathematical models and conversion
by chromatographic separation, and to lack of
factors that compensate for syrup composition.
the large crop production industry needed to
Glucose-containing syrups are sold at concen-
produce inulin. While the Jerusalem artichoke
trations usually varying between 75 and 85 wt %
is reported to produce tuber yields as high as
solids. Glucose–fructose syrups are usually pro-
100t/ha [86], present commercial sources of in-
duced at 71 – 75 wt % solids for the 42 % fruc-
ulin are primarily obtained from chicory [87].
tose syrup and 75 – 77 wt % solids for the 55 %
While some fructose is being produced, much of
fructose product. The moisture content of dry
the inulin is partially enzymatically hydrolyzed
products (crystalline glucose and solid glucose
18 Glucose and Glucose-Containing Syrups

syrups) is usually measured by weight loss under
vacuum drying or by Karl Fischer titration.
The carbohydrate composition of glucose
and glucose–fructose syrups is almost always
measured by high performance liquid chro-
matography (HPLC). The carbohydrate compo-
sition can be related to the traditional dextrose
equivalent (DE) by calculation [69]. However,
direct measurement is still practiced by using
copper reduction (the Lane and Eynon method)
[70].
The color of syrups is generally measured by
the amount of light transmitted through (or ab-
sorbed by) a fixed depth of syrup. The wave-
length of the light beam is chosen to be most
sensitive to soluble impurities such as ash. Most
syrups are referred to as “water white”; their
color content is so low that it is difficult to dis-
tinguish (visually) between syrups and water.
8. Legal Aspects
The legal aspects of glucose-containing products
are governed by a number of regulations defined,
in part, by such references as the U.S. Code
of Federal Regulations, the Codex Alimentarius
Commission, and the U.S. and British Pharma-
copeia. In the United States, glucose syrups and
monohydrate and anhydrous crystalline glucose
are considered standardized foods by the U.S.
Food and Drug Administration, while fructose
syrups derived from glucose are considered as
GRAS (generally regarded as safe) with speci-
fications defined by the Food Chemicals Codex
of the National Academy of Sciences.
level they are defined as maltodextrins). The
CFR requires that crystalline glucose have a DE
value no less than 99.5 [66].
Impurity Content. Ash content limits of 1
wt % for syrups (Codex Alimentarius) and 0.25
wt % for food-grade crystalline glucose (CFR)
are met easily by modern ion-exchange refin-
ing. The U.S. Pharmacopeia places much stricter
specifications (including specific rotation, acid-
ity, residue after ignition, and content of chlo-
ride, sulfate, arsenic or other heavy metals,
and other components) on pharmaceutical-grade
glucose [72].
9. Storage and Transportation
Storage temperatures of glucose-containing
syrups are a compromise between low tempera-
tures to minimize color development with time
(see Fig. 12) and high temperatures either to re-
duce the viscosity of low-DE syrups below 15.0
Pa s (to allow handling with lobe or vane pumps)
or to prevent crystallization of glucose in higher
DE syrups. Suggested temperatures for various
syrups are shown in Table 10.

Solid Concentration. The Codex Alimenta-

rius Commission recommends that the solids
content of glucose-containing syrups be no less
than 70 wt %. The U.S. Code of Federal Regula-
tions (CFR) specifies that anhydrous crystalline
glucose contain no less than 98 wt % dry sub-
stance (in practice, the commercial product usu-
ally contains < 0.1 wt % water) and that mono-
hydrate crystalline glucose contain no less than
90 wt % dry substance (in commercial practice, Figure 12. Glucose-containing syrup color as a function of
dry substance ranges between 91 and 92 wt %). time and temperature
a) 54 ◦ C; b) 49 ◦ C; c) 38 ◦ C; d) 27 ◦ C
Carbohydrate Composition. The Codex
Alimentarius recommends that glucose syrups Shipping containers for syrups range in size
have a DE value not lower than 20 (below this from 200 L drums to jumbo railcars holding 90 t.
 Glucose and Glucose-Containing Syrups
Table 10. Storage conditions of glucose-containing syrups
Syrup type Solids content, wt %
42 DE 80
83
60 DE 82
84
95 DE 71
42 HFCS 71
55 HFCS 77
90 HFCS 80
Liquid glucose (99.5 DE) 71
Trucks carrying 25 t are also used. Alternatives
to drums include 1000 L disposable containers
consisting of reinforced corrugated board outer
containers holding a heavy-duty plastic bag.
Bags for storage of crystalline glucose and
solid syrups must be protected against atmo-
spheric moisture pickup by incorporation of
a vapor barrier in the bag construction. Stor-
age temperatures of solid products should be
lower than 40 ◦ C and rapid temperature changes
should be avoided to minimize product caking.
Crystalline glucose is shipped in vapor-
resistant bags usually containing 50 or 100
pounds (or the approximate metric equivalent
sizes of 20, 25, and 40 kg) and in bulk trucks
and railcars (jumbo railcars can hold as much
as 82 t). Reusable containers holding about 1
t of crystalline material are used for customers
who do not require bulk delivery and who do not
want the bother and expense of bag opening and
disposal.
10. Uses
Glucose-containing syrups and glucose are used
in a variety of food and nonfood applications.
The manufacturing flexibility provided by enzy-
matic conversion techniques, coupled with mod-
ern refining and concentrating technology, pro-
vides a wide range of properties useful to the
food formulator. Table 1 illustrates the relative
volumes of usage in major food industries in the
United States. The impact of the introduction
of glucose–fructose syrups on other glucose ap-
plications can also be seen from this table. The
rapid and complete fermentation of glucose is a
valuable property in the fermentation and baking
industries. In countries where its use is permitted
by law, glucose is used by the brewing industry.
Glucose also serves as a raw material for the
manufacture of food-grade acids (citric, lactic,
19
Temperature, ◦ C Limiting condition
38 viscosity
49 viscosity
32 viscosity
41 viscosity
49 crystallization
32 crystallization
27 crystallization
16 crystallization
52 crystallization
acetic, etc.), enzymes, amino acids, vitamin C,
and a variety of antibiotics.
The largest nonfood use of unrefined glucose-
containing syrups is as a carbohydrate source
for the production of fuel-grade ethanol (→
Ethanol, Chap. 5.1.2). In 1986, the annual pro-
duction capability in the United States was re-
ported to be ca. 2.7×109 L [73] and a 1988 arti-
cle indicated a capacity of 3.9×109 L annually
[74]. Annual U.S. production capacity in 2006
was reported as 1.68×1010 L [75]
In other applications, the dehydration of glu-
cose to 5-hydroxymethylfurfural allows the in-
corporation of glucose-containing syrups into
phenolic and urea – formaldehyde-based plas-
tics [76]. Heating glucose and methanol in the
presence of anhydrous hydrogen chloride yields
α-methyl-d-glucoside which is used for insulat-
ing foams. Catalytic hydrogenation of glucose
yields sorbitol.
Glucose-bearing syrups are also added to ad-
hesives to improve stability and flow control,
used as humectant in wallboard and tobacco
manufacture, added to tiles and bricks to pre-
vent cracking during manufacture, used to retard
setting in concrete, are applied in resin and dye
manufacture and leather tanning to name but a
few of their nonfood uses.
11. Economic Aspects
The economics of starch-based sweeteners are
related to the economics of sucrose (cane and
beet sugar) except for uses in which produc-
tion costs and unique functionality allow higher
prices (such as high-purity crystalline glucose
for intravenous injection) or significant compe-
tition causes price reduction (such as glucose
syrups in the United States). In countries where
20 Glucose and Glucose-Containing Syrups
no protective tariff exists and sucrose is sold es-
sentially at world prices, the domestic consump-
tion volume of starch-based sweeteners depends
on sucrose pricing. For non tariff nations, con-
sumption and pricing figures can vary signifi-
cantly from year to year. The production and
pricing of starch-based sweeteners around the
world are shown in Table 11.
Raw material (starch) pricing is also an
important factor. Competition of markets for
starch-based products, primarily used for the
production of high-fructose syrups and fermen-
tation to fuel-grade ethanol has become impor-
tant in recent years. The impact of these two
products on the growth of the corn wet milling
industry in the United States is shown in Figure
13. In 2004, corn (maize) consumption for eth-
anol production amounted to more than half of
that consumed by all food and industrial uses in
the United States. While the food and industrial
use of maize in the United States has grown sub-
stantially since the 1970s, farm production has
more than kept up. The price of maize during
this period has trended downward (see Fig. 14).
Figure 13. Growth of corn wet miller’s shipments in the
United States 1929-2005, comprising starch, refinery prod-
ucts, fuel ethanol and coproducts
Figure 14. Average annual corn and net corn price 1 bushel
corn = 25.4 kg
But the real cost of maize to starch-based
sweetener manufacturers is the cost of maize
(corn) minus the income from the sale of co-
products of the wet milling process (corn gluten
feed, corn gluten meal, and corn oil), i.e., the net
corn cost. Year-to-year, net corn cost has fol-
lowed corn price in the USA since the 1970s
but the trendlines for corn and net corn cost are
converging, indicating an average reduction in
coproduct credit of 37 cents per bushel over the
past 30 years (see Fig. 14.). The rapid growth
in starch use in non-sweetener applications and
the impact on raw material cost and the price
of glucose-bearing products has been analyzed
[77, 78]. To date, it appears that agricultural pro-
ductivity increases have more than kept up with
expanding food and industrial use of maize in
the United States, keeping maize cost stable. For
wet millers in the USA, increased volumes of
coproduct have negatively impacted their prices,
primarily for corn oil and corn gluten feed. Since
fuel ethanol production is expected to nearly
double by 2012, net corn cost must be watched.
12. Physiological Properties and
Toxicology of Glucose
Glucose is absorbed into the bloodstream and
used by the body (via the glycolytic cycle)
for energy production or converted into other
metabolic intermediates required for growth or
maintenance of body tissues. By polymeriza-
tion into glycogen (a highly branched macro-
molecule referred to as body starch), it is also
stored in the liver for future use.
Glucose (and other sugars) acts as a dietary
chelating agent under certain conditions, bind-
ing iron and several other di- and trivalent met-
als [79]. Simultaneous ingestion of glucose and
a calcium supplement is reported to boost the
body’s uptake of that mineral by 25 % [80].
Blood serum cholesterol and phospholipid levels
are reportedly lowered within days of beginning
a high-glucose, lipid-free diet, whereas single
doses of glucose syrup may be responsible for
improved intellectual performance [81].
The lethal dose of glucose has been reported
as 20 g/kg of body weight when administered
orally to rabbits (the lethal intravenous dose for
the rabbit is 15 – 35 g/kg). The lethal oral dose
for dogs is ca. 8 – 12 g/kg [82].
 Glucose and Glucose-Containing Syrups 21
Table 11. Production and pricing of starch-based sweeteners by country (all production values in 103 t of dry substance per year, 1996
values used except where noted.)
Country Glucose syrups Maltose syrups Crystalline glucose Total sugar Fructose-glucose syrup
Monohydrate Anhydrous 42 % 55 %
United States
Production 3200 645 25 68 2300 5000
Price, US$/kg d.s. 0.30 0.62 1.25 0.88 0.41 0.45
Europe (EU 15)
Production 2200a b 320a b 45 330a b
Price, US$/kg d.s. 0.73c 0.96a 0.88 0.69c
Canada
Production 118d 300e
People’s Republic of China
Production 250 100 250f 50 100e
Price, RMBf /kg d.s. 4 4 6 3 6h
Japan
Production 440a i 35d d 39d d 44d d 845a e
Price, Yen/kg d.s. 34a 46a 95a 126a 113d 48a 54a
Latin Americad
Production 285 9 36 155
Price, US$/kg d.s. 0.30 2.86 0.17 0.40
Korea
Production 200j 33d k 3d k 55d k 250e l
Price, Won/kg d.s. 384l 420l 420l 390m 390l
South Africa
Production 175i 3
Price, US$/kg d.s. 0.43n 0.68
Australiao
Production 57 4.3
Malaysiao
Production 3.8 2.4
Price, US$/kg d.s. 0.57 0.59
Bangladeshp
Production 3.5 1.0
Price, US$/kg d.s. 0.54 0.64
a
1995 data.
b
90+% of the volume shown is sold within the EU15; less than 10% is sold in other European countries.
c
1983 data.
d
1986 data.
e
Combined production of 42 % db and 55 % db fructose-bearing syrups shown.
f
Most crystalline (pure) dextrose is monohydrate, some is anhydrous. Main uses are medical in nature.
g
J. At the time of the preparation of this chart, US$1.00 = 8.5 RMB.
h
Price for 42 % db fructose syrup shown; only one known producer of 55 % fructose syrup in the P.R.C.
i
Combined production data for glucose and maltose syrups.
j
1992 data.
k
Totals for the production of these three products in 1992 virtually unchanged from 1986, individual product data not available in 1992 so
1986 values are shown.
l
1994 data.
m
1991 data.
n
1987 data.
o
1996 list price for 43 DE glucose syrup.
p
2005 data.

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 Glycerol 1

Glycerol
Ralf Christoph, Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
Bernd Schmidt, Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
Udo Steinberner, Cognis Deutschland GmbH, Düsseldorf, Federal Republic of Germany
Wolfgang Dilla, Solvay Soda Deutschland GmbH, Rheinberg, Federal Republic of Germany
Reetta Karinen, Helsinki University of Technology, Finland

1. Introduction . . . . . . . . . . . . . . . 1 6. Quality Specifications and Analysis 11

2. Physical Properties . . . . . . . . . . . 2 7. Storage and Transportation . . . . . 12
3. Chemical Properties . . . . . . . . . . 4 8. Derivatives . . . . . . . . . . . . . . . . 12
4. Production . . . . . . . . . . . . . . . . 4 8.1. Esters . . . . . . . . . . . . . . . . . . . . 12
4.1. Glycerol from Fats and Oils . . . . . 5 8.2. Chlorohydrins . . . . . . . . . . . . . . 12
4.1.1. Fat Splitting . . . . . . . . . . . . . . . . 5 8.3. Oxidation Products . . . . . . . . . . . 12
4.1.2. Pretreatment and Concentration of 8.4. tert-Butyl Ethers . . . . . . . . . . . . 12
Crude Glycerol . . . . . . . . . . . . . . 5 9. Use of Glycerol and its Derivatives . 13
4.1.3. Purification and Refining . . . . . . . . 6
9.1. Use in Foods, Cosmetics, and
4.2. Synthesis from Propene . . . . . . . . 8
Pharmaceuticals . . . . . . . . . . . . . 13
4.2.1. Production from Allyl Chloride . . . . 8
9.2. Use in Plastics, Resins, and
4.2.2. Production from Acrolein . . . . . . . . 9
Cellophane . . . . . . . . . . . . . . . . 14
4.2.3. Production from Propylene Oxide . . 9
4.3. Other Processes . . . . . . . . . . . . . 9 9.3. Use in Tobacco Industry . . . . . . . 14
5. Environmental Protection . . . . . . 10 9.4. Other Applications . . . . . . . . . . . 14
5.1. Production from Fats and Oils . . . 10 9.5. Future Applications . . . . . . . . . . 14
5.2. Production from Epichlorohydrin . 10 10. Economic Aspects . . . . . . . . . . . . 14
5.3. Environmentally Important 11. Toxicology . . . . . . . . . . . . . . . . . 15
Properties of Glycerol . . . . . . . . . 11 12. References . . . . . . . . . . . . . . . . . 15

Abstract
Glycerol is the simplest triol. It can be found
in all natural fats and oils as fatty esters and is
an important intermediate in the metabolism of
living organisms. It is completely miscible with
water and many alcohols and also with many het-
erocyclic compounds. A remarkable and grow-
ing source of glycerol is as a byproduct in the
production of biodiesel. Glycerol is presently
used in a large variety of applications because of
its particular combination of chemical and phys-
ical properties and because it is physiologically
innocuous.
1. Introduction
Glycerol [56-81-5], C3 H8 O3 , M r 92.09, 1,2,3-
propanetriol, commonly known as glycerin, is
the simplest triol. It can be found in all natural
fats and oils as fatty esters and is an important
intermediate in the metabolism of living organ-
isms.
Glycerol was discovered in 1779 by Scheele
through saponification of olive oil with lead ox-
ide. In 1813, Chevreul showed that fats are glyc-
erol esters of fatty acids. He also gave glycerol
its name, after the Greek word γλυκoς which

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 477.pub2
2 Glycerol

means sweet. The first industrial use of glycerol

was in 1866 when Nobel produced dynamite, in
which the trinitrate of glycerol — nitroglycerin
— is stabilized by absorption on diatomaceous
earth.
The most important industrial synthesis of
glycerol, which uses propene as starting ma-
terial, was developed in the late 1930s by I.G.
Farben in Germany and by Shell in the United
States.
Glycerol is now used in a large variety of ap-
plications because of its particular combination
of chemical and physical properties and because
it is physiologically innocuous. Total production
is estimated (1998) to be ca. 750 000 t/a; about
90 % is produced by processing natural oils or
fats and 10 % is synthesized from propene [1, 2].

2. Physical Properties
Glycerol is a sweet-tasting hygroscopic liquid;
when pure, it is colorless and odorless. At room Figure 1. Vapor pressure of glycerol – water solutions
(wt % glycerol) [7, 10]
temperature it is viscous.
The boiling point of glycerol is 290 ◦ C at
atmospheric pressure (101.3 kPa). The corre-
sponding values under reduced pressure are
listed in Table 1. With some liquids, (e.g., bi-
phenyl), glycerol forms azeotropes; with oth-
ers (e.g., water), nonazeotropic mixtures are
formed. The vapor pressure curves of glycerol
– water solutions at various glycerol concentra-
tions are shown in Figure 1. The liquid – vapor
equilibria of glycerol – water solutions, impor-
tant for distillation and fractionation, have been
established experimentally [3 – 5]. The boiling-
and condensing curves at 13.3 and 1.33 kPa are
shown in Figure 2. Suitable theoretical methods
of calculation are also available [6].
Table 1. Vapor pressure vs. temperature of glycerol Figure 2. Liquid–vapor equilibria for glycerol–water so-
lutions
Temperature, ◦ C Pressure, kPa a) Boiling curve, 1.33 kPa; b) Boiling curve, 13.3 kPa;
c) Condensing curve, 1.33 kPa; d) Condensing curve, 13.3
290 101.3
kPa
266 53.3 The freezing point of pure glycerol is ca.
18 ◦ C. The crystalline state is seldom reached,
222 13.3
204 6.67
175 2.00 however, because of a strong tendency toward
152 0.67 supercooling. A solid, glassy state can be ob-
130 0.18
served from ca. − 70 to − 110 ◦ C. Crystalliza-
100 0.03
20 <0.0001 tion can be brought about at ca. 0 ◦ C by seed-
ing with glycerol crystals. The freezing point

of glycerol – water solutions is shown in Figure
3. At 66.7 wt % glycerol, an eutectic mixture is
formed, fp − 46.5 ◦ C.
Figure 3. Freezing point of glycerol–water solutions
The density of glycerol is 1.261 g/cm3
(20 ◦ C). Tables of the density of glycerol – wa-
ter solutions at various concentrations of glyc-
erol are given in [7]. For rough estimations, a
mean density change of 0.0007 g/cm3 per unit
change in temperature may be used in the range
from 0 to 200 ◦ C. The compressibility of glyc-
erol is only about half that of water.
Figure 4. Dynamic viscosity of glycerol – water solutions
Glycerol 3
The refractive index of aqueous glycerol for
the range 0 – 100 % glycerol is tabulated in 1 %
steps in [7]. The viscosity of glycerol – water
solutions (0 – 100 wt % glycerol) from − 40 to
100 ◦ C has been determined [7]. Some curves
are shown in Figure 4. Aqueous glycerol solu-
tions, at any concentration, will supply moisture
until equilibrium with water vapor in the atmo-
sphere is reached [7]. The relative humidity over
glycerol solutions is illustrated in Figure 5.
Figure 5. Relative humidity over aqueous glycerol (20 –
100 ◦ C)
Glycerol has useful solvent properties, sim-
ilar to those of water and simple aliphatic al-
cohols, because of its three hydroxyl groups. It
is, accordingly, completely miscible with water,
methanol, ethanol, and the isomers of propanol,
butanol, and pentanol. It is also fully misci-
ble with phenol, glycol, propanediols, amines,
and heterocyclic compounds containing a ni-
trogen atom in the ring (e.g., pyridine, quino-
line). Its solubility, however, is limited in ace-
tone, diethyl ether, and dioxane. Glycerol is
almost insoluble in hydrocarbons, long-chain
aliphatic alcohols, fatty oils, and halogenated
solvents such as chloroform. Ternary systems,
such as glycerol – water – phenol and the non-
aqueous system glycerol – ethanol – benzene,
display significant temperature-dependent mis-
cibility gaps. Glycerol also forms azeotropes
with some other substances [8]. Glycerol is a
useful solvent for many solids, both organic and
4 Glycerol

inorganic (e.g., see Table 2), which is particu- terminal primary hydroxyl groups are slightly
larly important for the preparation of pharma- more reactive than the internal secondary hy-
ceuticals. The solubility of gases in glycerol, droxyl group. In the presence of small amounts
like other liquids, is temperature- and pressure- of strong mineral acid the odor of acrolein (odor
dependent [9]. Some important physical proper- threshold 0.2 – 0.4 ppm) is already quite percep-
ties of glycerol are presented in Table 2; a com- tible at 160 ◦ C. At 200 ◦ C and more the forma-
prehensive collection of data is available [10]. tion of acrolein is vigorous. When heated un-
der neutral or alkaline conditions, only traces of
Table 2. Physical properties of glycerol
acrolein have been observed. At 180 ◦ C, alka-
line glycerol begins to dehydrate, forming ether-
Mr 92.09 linked polyglycerols. At room temperature glyc-
mp 18.0 ◦ C erol rapidly absorbs water; when dilute it is at-
bp (101.3 kPa) 290.0 ◦ C
Density (20 ◦ C) 1.261 g/cm3
tacked by microorganisms. Glycerol is easily ox-
Refractive index n20
D 1.4740 idized: the terminal carbon atoms to aldehyde or
Dynamic viscosity (20 ◦ C) 1.410 Pa · s carboxyl groups and the central carbon atom to a
Compressibility (28.5 ◦ C) 2.1×10−4 MPa−1 carbonyl group [11, 12]. Biochemical oxidation
Gravity coefficient of thermal
expansion (15 – 20 ◦ C) 0.000615 K−1
of glycerol has also been described [13]. Cat-
Surface tension (20 ◦ C) 63.4 mN/m alytic hydrolysis [14] or microbial conversion
Heat of formation −669 kJ/mol [15] of glycerol to acrolein and 1,3-propanediol
Heat of combustion −1662 kJ/mol
was also a topic of research.
Heat of vaporization (55 ◦ C) 88.2 kJ/mol
(195 ◦ C) 76.1 kJ/mol Industrially important reaction products of
Heat of fusion (18 ◦ C) 18.3 kJ/mol glycerol include:
Heat of solution (infinite dilution) − 5.8 kJ/mol
Heat capacity (298 K < T < 383 K) C p (T ) = 987.98 + 1) Mono-, di-, and triesters of inorganic and or-
4.7074×T in J ganic acids;
kg−1 K−1
(− 80 ◦ C) 1.91 kJ kg−1 K−1
2) Mono- and diglycerides of fatty acids formed
(− 108 ◦ C) 0.91 kJ kg−1 K−1 by transesterification of triglycerides (from
Thermal conductivity (0 ◦ C) 0.29 W m−1 K−1 fats);
Diffusion constant of water into 3) Aliphatic and aromatic esters, formed by re-
glycerol (20 ◦ C) 1.33×10−11 m2 /s
Specific electrical conductivity
action with alkylating or arylating agents, re-
(20 ◦ C) 0.1 µS/cm spectively [16, 17];
Relative dielectric constant (25 ◦ C) 42.48 4) Polyglycerols, formed by reaction of glycerol
Flash point 177 ◦ C and epichlorohydrin with consecutive alka-
Fire point 204 ◦ C
Autoignition temperature on glass 429 ◦ C line hydrolysis or by intermolecular elimina-
Calorific value 18 kJ/g tion of water with alkaline catalysts;
Solubility of KCl (99.5 % glycerol) (25 ◦ C)6.01 g/100 g 5) Cyclic 1,2- or 1,3-acetals or ketals, formed by
(90 ◦ C) 8.78 g/100 g
Solubility of NaCl (99.5 % glycerol) 7.22 g/100 g
reaction with aldehydes or ketones, respec-
◦
(25 C) tively;
◦
(90 C) 7.31 g/100 g 6) Mono- or diglycerates, formed by the action
Solubility of Na2 SO4 (99.5 % glycerol) 0.20 g/100 g of alkali or metal alcoholates.
(25 ◦ C)
(90 ◦ C) 0.63 g/100 g 7) Glycerol polyoxyalkylenes, formed by
Solubility of N2 (99.25 % glycerol)
◦
0.553 vol % alkoxylation of glycerol(s) with ethylene-
(15 C)
or propylene oxide under alkaline conditions.
Solubility of CO2 (99.26 % glycerol) 43.8 vol %
(15 ◦ C) In addition to these, there is a growing inter-
est to oxidation products of glycerol and ethers,
especially tert-butyl ethers (see Chapter 8).

3. Chemical Properties
Glycerol is a reactive molecule that undergoes
all the usual reactions of alcohols (→ Alcohols,
Aliphatic; → Alcohols, Polyhydric). The two
4. Production
Glycerol is obtained as a byproduct in the con-
version of fats and oils to fatty acids or fatty acid

methyl esters. This type of glycerol is known
as natural or native glycerol, in contrast to syn-
thetic glycerol from propene. Other methods of
production (e.g., fermentation of sugar or hydro-
genation of carbohydrates) are not industrially
important.
The fastest growing source of glycerol is
the production of fatty acid methyl esters for
biodiesel (see → Automotive Fuels). In Europe
alone the production in 2004 was 1.5 × 106 t and
it is expected to increase to over 10 × 106 t by
the year 2010. Per each tonne of biodiesel 100
kg of glycerol is formed.
In Europe the legislation requires the use of
renewable components in fuels and another im-
portant factor enhancing the biodiesel introduc-
tion is the fact that for many countries it is pro-
duced from domestic raw material and thus it
reduces the dependence from the imported oil.
It is also an environmentally friendly source of
energy.
4.1. Glycerol from Fats and Oils
Although a component of all vegetable and an-
imal fats and oils, glycerol does not exist in the
free form but as fatty acid esters; all three hy-
droxyl groups are usually esterified. Such esters
are called triglycerides (→ Fats and Fatty Oils;
→ Fatty Acids). The glycerol content of fats and
oils varies between 8 and 14 wt %, depending
on the proportion of free acid and on the chain-
length distribution of the fatty acid esters. To
obtain glycerol, the oils and fats must be split
hydrolytically.
4.1.1. Fat Splitting
(For a detailed description of processes used in
the splitting of fats and oils see → Fatty Acids,
Chap. 3)
Natural glycerol today is mainly produced by
high-pressure splitting and transesterification.
Glycerol from the neutral saponification of oils
is encountered only in small quantities.
High-Pressure Splitting. Splitting under
pressure has been known since 1854; contin-
uous process reactors are now used. Water and
fat are fed into a splitting column in counter-
current fashion at 2 – 6 MPa and 220 – 260 ◦ C,
Glycerol 5
leading to a ca. 15 % solution of glycerol in
water, known as sweet water. This glycerol is
marketed as 88 % saponification- or hydroly-
sis-crude glycerol. Such glycerol is extremely
low in ash: a typical value is ca. 0.1 % or less of
inorganic salts.
Transesterification. Natural crude glycerol
of similar quality can be obtained from the trans-
esterification (either high or low pressure regime
[18]) of oils and fats to their methyl esters. Con-
tinuous processes are dominating. Glycerol from
the low pressure transesterification process has
a much higher salt content of 2 – 5 %. The crude
glycerol is obtained directly at a concentration
of ca. 90 – 92 %.
Saponification. The splitting of fats by
saponification of neutral oils is a traditional
method; caustic alkali or alkali carbonates are
used, as in the production of soap (→ Soaps).
The use of calcium hydroxide in the form of
milk of lime is also possible.
4.1.2. Pretreatment and Concentration of
Crude Glycerol
The pretreatment of glycerol water is an im-
portant step in the work-up, which is crucial
for trouble-free production and for the quality
of the final product. Glycerol water produced
by high-pressure hydrolysis is slightly acidic.
Dispersed fat and fatty acid components can be
largely removed under these conditions simply
by settling or by centrifugation. In a subsequent
step the concentration is immediately increased
to 70 – 90 % glycerol to avoid decomposition by
fermentation (resulting in formation of 1,3-pro-
panediol) and to render the crude product sta-
ble to storage. A multistage flash evaporator of
stainless steel yields the greatest economic ad-
vantage. This main pretreatment takes place di-
rectly before final purification and refining.
An optimum treatment effect can be obtained
in dilute solutions with a glycerol content of
ca. 50 %. A two-step process is normally em-
ployed. Activated carbon and sodium hydroxide
are used as auxiliaries, the former for bleach-
ing and absorption of impurities, the latter to
saponify any remaining fat components. A sep-
aration by filtration follows each step. The so-
called soda-lime process has been valued for
6 Glycerol
Figure 6. Continuous glycerol distillation (Crown Iron Works Company)
a) Economizer; b) Circulation heater (reboiler); c) Crude still; d) Reflux cooler; e) Dosing system; f) Pitch still; g) Condenser;
h) Deodorizer column; i) Cooler; j) Bleaching column; k) Polishing filter
decades for the pretreatment of crude glycerol
contaminated with larger amounts of organic im-
purities [7]. The treated crude glycerol is further
concentrated by distillative work-up. Single- or
multiple-step plants are used with a vacuum of
10 – 15 kPa. The solubility limits of the salts
must be taken into consideration, and the rel-
evant stages suitably equipped for removal of
the salt.
Desalination of crude glycerol is also pos-
sible by ion exclusion chromatography, using
a cationic, strongly acidic exchange resin. The
technique was originally developed in the sugar
industry. The resin column is first fed with
a certain amount of glycerol, the ionic sub-
stances remain in the liquid volume between the
resin particles (Donnan effect), whereas the non-
ionic components concentrate in the resin pores.
When the resin column is rinsed with water in
the second step, the ionic substances are eluted
first, followed by the nonionic compounds [19,
20]. By measuring density and conductivity, the
process steps can be run completely automati-
cally.
4.1.3. Purification and Refining
Until the end of the 1950s the large-scale pro-
duction of pharmaceutical-grade glycerol was
possible only by distillation. Batches were dis-
tilled under vacuum with fractional condensa-
tion. The development of new technologies al-
lowed conversion to continuous production pro-
cesses, with correspondingly low losses.
A glycerol refining unit used for the ther-
mal work-up of crude pretreated and evaporated
glycerol to glycerol of 99.5 % purity is shown in
Figure 6 [21, 22]. For work-up of glycerol with
a high salt content, ion exclusion chromatogra-
phy [23] (see Section 4.1.2) or thin-film dis-
tillation is employed [24, 25]. The glycerol is
spread by a rotor in a thin film onto the inner
wall of an externally heated column and vapor-
ized. The residue flows or trickles to the bottom.
This equipment, combined with a fractionating
column, is shown in Figure thin-film distillation
is the extremely short residence time; thermal
loading of the glycerol is thereby minimized. Re-
finement of diluted (40 – 50 % glycerol) low-salt
crude glycerol can also be carried out by ion ex-
change (see Fig. 8). This process became avail-
able with the development of exchange resins

Figure 7. Continuous glycerol distillation (Cognis) [25]
a) Economizer; b) End heater; c) Thin-film distillation; d) Fractionating column; e) Reboiler; f) Reflux condenser; g) Glycerol
condenser; h) Water condenser
Figure 8. Ion exchanger (principle diagram)
suitable for glycerol [26]. Ion exchangers are
used in pairs and consist of a cationic and an an-
ionic exchanger. Charged impurities are thereby
successively removed and ultimately exchanged
for water. The process permits removal of inor-
ganic salts, fat and soap components, colored
matter, odor-causing substances, and other im-
purities. The so-called adsorption resins possess
special decolorizing properties; nonionic com-
Glycerol 7
ponents such as chromophores can be removed
physically by adsorption [27, 28].
The subsequent concentration of
pharmaceutical-grade glycerol solutions is car-
ried out under especially mild conditions to
avoid changes in color and odor: a three- or
four-step stainless steel flash evaporator with
natural circulation is mostly used (Fig. 9).
8 Glycerol
Figure 9. Continuous glycerol concentration
a) Feed heater; b) Evaporator; c) Separator with demister; d) Water condenser; e) Glycerol heater; f) Glycerol heater/final
product cooler; g) Falling film evaporator; h) Glycerol condenser
At 10 – 15 kPa, a glycerol concentration of
ca. 90 – 95 % is attained. The removal of resid-
ual water to give a glycerol concentration >
99.5 % is best carried out in a separate final step
by forced circulation in a falling-film evaporator.
The vacuum used is 0.5 – 1.5 kPa. The contin-
uous processes described above are suitable for
automation when equipped with the appropriate
control equipment.
4.2. Synthesis from Propene
Three processes are known for the production of
glycerol from propene [115-07-1], involving the
following intermediate stages (Fig. 10):
1) Allyl chloride – epichlorohydrin
2) Acrolein – allyl alcohol – glycidol
3) Propylene oxide – allyl alcohol – glycidol
Only the first of these is important industrially.
4.2.1. Production from Allyl Chloride
The first synthetic glycerol was produced in
1943 by I.G. Farben in Oppau and Heydebreck
and in 1948 by Shell in Houston, Texas. This
method became available once the high-tempe-
rature chlorination of propene to allyl chloride
[107-05-1] could be controlled properly (→ Al-
lyl Compounds, Chap. 1.3.1). The allyl chloride
produced is oxidized with hypochlorite to di-
chlorohydrin, which is converted without isola-
tion to epichlorohydrin [106-89-8] by ring clo-
sure with calcium or sodium hydroxide (→ Ep-
oxides, Chap. 4.1). Hydrolysis to glycerol is car-
ried out with sodium hydroxide or sodium car-
bonate [29 – 31].
Epichlorohydrin is hydrolyzed to glycerol at
80 – 200 ◦ C with a 10 – 15 % aqueous solution
of sodium hydroxide or sodium carbonate at at-
mospheric or overpressure. The residence time
in one or a series of several closed, continuously
operating reactors amounts to several minutes or
several hours depending on the plant concerned.
The yield of dilute (10 – 25 %) glycerol solu-
tion is > 98 %. The solution contains 5 – 10 %
sodium chloride and less than 2 % of other impu-
rities (Fig. 11). This aqueous glycerol solution
containing sodium chloride is evaporated in a
multistage evaporation plant under vacuum to a
glycerol concentration of > 75 %; precipitated
sodium chloride is separated at the same time
(Fig. 12). The glycerol solution is then distilled
under high vacuum (ca. 0.5 – 1.0 kPa) as shown,
e.g., in Section 4.1.3, Figs. 6 and 7; codistilled
water is separated by fractional condensation.
Residual inorganic salts and higher oligomers

Figure 10. Routes for synthesis of glycerol from propene
of glycerol remaining after the evaporation must
be worked up further or discarded. The glycerol,
practically free of water, is treated further to re-
move colored impurities and odorous material;
this can be performed, for example, with acti-
vated carbon.
Figure 11. Synthesis of glycerol from epichlorohydrin
a) Exhaust gas cooler; b) Circulation reactor
4.2.2. Production from Acrolein
The acrolein process for the production of glyc-
erol was developed by Shell and does not re-
quire the use of chlorine [32]; the first plant was
built in 1958 in Norco, Louisiana. Propene is
oxidized to acrolein [107-02-8], which is then
reduced to allyl alcohol [107-18-6] (Meerwein–
Ponndorf–Verley reduction). The allyl alcohol
is epoxidized with hydrogen peroxide, and the
Glycerol 9
resulting glycidol [556-52-5] is hydrolyzed to
glycerol.
4.2.3. Production from Propylene Oxide
As with acrolein, preparation of glycerol from
propylene oxide does not use chlorine. Propene
is epoxidized to propylene oxide, which is then
isomerized to allyl alcohol by the Progil pro-
cess [33] (→ Allyl Compounds, Chap. 2.3.2). A
second epoxidation is carried out with peracetic
acid, and the resulting glycidol is hydrolyzed to
glycerol.
4.3. Other Processes
Fermentation of Sugar. The formation of
glycerol by fermentation of alcohol was disco-
vered in 1858 by Pasteur. Industrial use became
possible once the mechanism was understood;
the fermentation could be interrupted at the glyc-
eraldehyde 3-phosphate stage with sodium car-
bonate or with alkali or alkaline earth sulfites.
After reduction to glycerol phosphate, glycerol
is obtained in yields up to 25 % by hydrolysis
[34 – 37]. The process is economically unim-
portant.
Hydrogenation of Carbohydrates. Hydro-
genation of natural polyalcohols such as cellu-
lose, starch, or sugar leads to mixtures of glyc-
erol and glycols, which can be separated by dis-
tillation. Catalysts used in this high-temperature
10 Glycerol
Figure 12. Three-stage evaporation plant for aqueous glycerol solutions: Buss glycerol evaporation process [24]
a) Evaporator vessel; b) Reboiler; c) Cyclone; d) Vacuum pump; e) Centrifuge; f) Stirred tank; g) Storage tank for glycerol
solution
reaction include nickel, copper, cobalt, chromi-
um, and tungsten, as well as oxides of some of
the lanthanides [38].
Other Noncommercial Processes. Glycerol
can be obtained in yields of ca. 7 % by enzymatic
splitting of fats and oils with lipases in special
reactors [39 – 41] (→ Fatty Acids, Chap. 3.2.3).
Photoproduction of glycerol along with other
biomass is possible by means of solar energy
and algae [42, 43]. Another synthetic process
involves the catalytic hydrogenation of carbon
monoxide [44].
5. Environmental Protection
Ecologically, glycerol presents no special prob-
lems. Discussion of environmental protection is
limited to those industrial processes based on
fats and oils and on epichlorohydrin, because
only these processes are economically impor-
tant.
5.1. Production from Fats and Oils
Production Plants. No special protective
measures are necessary for the work-up of natu-
ral crude glycerol with the technology described
above.
Gaseous Emissions. Certain measures are
necessary to prevent atmospheric pollution by
odors during storage and purification of native
crude glycerol. Exhaust vapor from the respec-
tive tanks and process units should be drawn off
and treated (e.g., burned) in a closed system (→
Fatty Acids, Chap. 7).
Residues. The residues of higher glycerol
oligomers and inorganic salts remaining from
evaporation and distillation are water soluble
and must be treated further, recycled, or disposed
of properly.
5.2. Production from Epichlorohydrin
Extensive protective measures must be taken to
allow proper handling of epichlorohydrin, be-
cause of the hazardous properties of this mate-
rial (→ Epoxides). Regulations exist in several
countries concerning exhaust gas and wastewa-
ter purification as well as measures for the pro-
tection of plant personnel.
Production Plants. Production plants must
be explosionproof to prevent ignition of
epichlorohydrin. Manipulation of epichlorohy-
drin exclusively in closed systems guarantees
protection of personnel.

Gaseous Emissions. Epichlorohydrin and
accompanying organic material in exhaust gases
from the hydrolysis of epichlorohydrin can be
removed, for example, by adsorption on acti-
vated carbon or can be incinerated.
Wastewater. Wastewater contaminated with
epichlorohydrin can be treated with alkali,
thereby converting the epichlorohydrin to glyc-
erol.
Residues. Residues from evaporation and
distillation should be treated as described in Sec-
tion 5.1.
5.3. Environmentally Important
Properties of Glycerol
Gaseous Emissions. No problems are en-
countered with gaseous emissions because of the
low vapor pressure of glycerol and the lack of
odor of the pure material.
Wastewater. Glycerol poses no problems for
wastewater because it is completely and read-
ily biodegradable in sewage treatment plants
according to OECD classifications. Glycerol is
not regarded as dangerous to the water supply:
the relevant values are: COD = 1217 mg of O2
per gram; BOD5 = 780 mg of O2 per gram. The
fish toxicity is >100 mg/L (LC50 according to
acute fish toxicity test OECD 203). Local regu-
lations regarding wastewater must be taken into
account.
6. Quality Specifications and
Analysis
Glycerol can be detected qualitatively by heat-
ing a small sample with potassium hydrogen sul-
fate; the presence of glycerol is indicated by the
characteristic pungent odor of acrolein.
The most accurate wet method for quantita-
tive determination of glycerol is periodate oxi-
dation. Glycerol is oxidized by sodium periodate
to formaldehyde and formic acid:
Glycerol 11
Formic acid is determined by titration and is a
measure of the amount of glycerol; polyols with
three or more neighboring hydroxyl groups (e.g.,
sugars) interfere. For quantitative determination
of impurities in glycerol gas chromatography is
employed.
Natural and synthetic glycerols can be distin-
guished by site-specific natural isotope fraction-
ation nuclear magnetic resonance spectroscopy
(SNIF – NMR) and isotope ratio mass spec-
troscopy (IRMS) [45, 46]. Water in glycerol
can be determined quantitatively by Karl Fis-
cher titration or by near infrared spectroscopy
(NIR). A rapid method for establishing the glyc-
erol content of commercial glycerol–water mix-
tures is measurement of the refractive index at
20 ◦ C or determination of the density with a dig-
ital instrument that electronically measures the
period of oscillation of a swinging body sus-
pended in the glycerol [47]. In contrast, mea-
surement of the density with a pycnometer is,
for the same degree of accuracy (0.1 %), con-
siderably more time consuming. Color is given
as Hazen or APHA color number; typical color
values would be 5 – 20, depending on the glyc-
erol quality. For rapid measurement, equipment
is available for direct color comparison with
standardized slides. Ash, heavy metals, chlo-
ride and organic chlorine compounds, pH, and
acidic or alkaline substances can be determined
by standard analytical methods or by methods
given in various pharmacopoeias. Traces of re-
ducing agents, such as aldehydes, sometimes
still present in glycerol can be determined quan-
titatively by special tests, e.g., with silver nitrate.
Glycerol is sold in crude (natural glycerol) or
pure form. In the latter, a distinction is made bet-
ween various grades that are linked with given
sets of specifications and analytical methods:
– Technical glycerol at various concentrations
(e.g., Nobel test glycerol 99.5 %, Glycerol
99.8 %)
– Pharmaceutical grade (e.g., Ph. Eur., U.S.P.,
Japanese Pharmacopoeia): Glycerol Ph. Eur.
85 %, Glycerol Ph. Eur.
– Food grades [e.g. E 422 (EU-directives
98/86/EC, 95/2/EC), Food Chemical Codex
grade (FCC); generally recognized as safe
(GRAS § 182.1320) for human consumption
by the U.S. FDA].
12 Glycerol

7. Storage and Transportation 8.3. Oxidation Products

Storage. Glycerol should preferably be
stored at 40 – 60 ◦ C under nitrogen blanketing. The oxidation products of glycerol are presented
It is not corrosive and presents little risk of ig- in Figure [13]. The components derived from
nition because of its high flash point. Highly glycerol are valuable intermediates for fine and
concentrated glycerol does not corrode steel, but specialty chemicals and some of them are useful
storage tanks of carbon steel must be protected as such. Their current and common production
by surface coating to prevent rusting by residual methods involve complex organic syntheses, fer-
moisture. Glycerol is therefore usually stored in mentation and multiple step reactions and the
tanks of stainless steel [48, 49] or aluminum. production costs are high and amounts of pro-
Regulations exist in some countri es to control duced waste are large. Selective catalysed reac-
the construction and arrangement of industrial tions from glycerol offer benefits in reduced pro-
storage tanks. ductions costs, increased selectivity and reduced
amounts of waste and solvents. Studies are con-
Transportation. Glycerol is shipped in tank centrated on heterogeneous catalysis and sup-
trucks, containers, and drums. The tank trucks ported platinum and palladium are regarded as
and containers are usually made of stainless the best catalysts for glycerol oxidation e.g.,[52,
steel. Galvanized or resin-coated steel as well 53]. Also supported gold catalysts [54] as well as
as plastic is used for drums. some homogeneous catalysts, such as TEMPO
(2,2,6,6-tetramethylpiperidine-1-oxyl) [55], are
studied.
8. Derivatives
8.1. Esters
Glycerol forms esters with both inorganic and
organic acids; depending on reaction conditions
and degree of esterification, these can be mono-,
di-, or triglycerides. Of most importance are es-
ters produced from nitric, acetic, and fatty acids
[7, 51].
Glycerol trinitrate [55-63-0], nitroglycerin,
is produced in a mixture of nitric and sulfuric
acids. It is used as an explosive and pharmaceu-
tical.
The acetins are produced industrially by es-
terification of glycerol with acetic acid, acetic
anhydride, or both. They are the most important
esters of glycerol from short-chain carboxylic
acids. The greatest use is of triacetin.
Glycerol fatty esters, the partial glycerides,
are obtained by transesterification of fats or oils
with glycerol to a mixture of mono- and diglyc-
erides. The mono- and diesters of fatty acids are
edible, as are the triglycerides. Figure 13. Oxidation products of glycerol

8.2. Chlorohydrins 8.4. tert-Butyl Ethers

Chlorohydrins are treated in a separate keyword Glycerol can be etherified with alkenes and es-
(→ Chlorohydrins); epichlorohydrin see → Ep- pecially etherification with isobutene to produce
oxides, Chap. 4.1.

tert-butyl ethers of glycerol is regarded inter-
esting [56 – 60]. Depending on the extent of
the etherification reaction various products are
formed. Altogether five isomers are formed as
1–3 hydroxyl groups in glycerol molecule can
be etherified and also isomers exist (Fig. [14]).
The product distribution can be controlled by
process conditions, e.g., temperature and feed
compo -sition.
Figure 14. tert-Butyl ethers of glycerol
9. Use of Glycerol and its Derivatives
Today, glycerol has more than 2000 different ap-
plications that arise from its properties: glycerol
is water-soluble, is odor- and colorless, has a cer-
tain sweetness, absorbs and retains water, has a
capacity to dissolve flavors and dyes, has plas-
ticizer properties, protects against fermentation
processes, has antioxidant properties, is non-
toxic and easily biodegradable and is a polyol.
Information on areas of application is available
in the literature [61]; over 800 references are
cited in [62] alone. Consumption of glycerol ac-
cording to major applications is shown in Figure
15.
Glycerol 13
Figure 15. Applications of glycerol (worldwide)
9.1. Use in Foods, Cosmetics, and
Pharmaceuticals
Foods. In beverages, syrups, and flavor ex-
tracts glycerol is applied as a solvent for the
preparation of concentrated flavor extracts from
natural products such as vanillin or spices. Fur-
thermore, it is a carrier for many dyes and syn-
thetic flavor compositions and has a good com-
patibility with sucrose for the preparations of
concentrated syrups. Glycerol as such or in the
form of its monoglycerides improve s the texture
and extends the shelf life of baked goods. Glyc-
erol is used as a conditioner for wine gums, fon-
dants, soft creams, or pastilles. Fruits and veg-
etables are sprayed with glycerol to keep them
in fresh conditions. Mono- and diglycerides are
main emulsifiers in ice-cream production, they
improve texture, stability and melting proper-
ties; in margarine, th ey improve texture and
water retention. Glycerol esters of acetic and tar-
taric esters are used as emulsifiers in bread pro-
duction; citric acid esters are used in sausages
and meat products, and lactic acid esters serve,
e.g., as emulsifier for desserts. Glycerol is ap-
plied as a moisturizer in sweets and dried fruits
to prevent loss of water followed by shrinkage
and is a preservative for fish, poultry, and meat
[62].
Cosmetics. In cosmetics and toiletries glyc-
erol is mainly used of its chemical properties
(formation of esters that serve as emulsifiers
or conditioners), moisturizing, and conditioning
14 Glycerol
properties. Glycerol finds application in creams,
lotions, and preparations for skin and hair care as
well as in tooth pastes and dental mouthwashes
[63].
Pharmaceutical applications of glycerol
arise from its conditioning, self-preserving, and
dissolving properties in syrups, ointments, and
parenteral solutions. Glycerol trinitrate is an
important drug for the treatment of angina pec-
toris. Glycerol also is used as a mild laxative in
suppositories. It is a softener in gelatin capsules
and suppositories [64].
9.2. Use in Plastics, Resins, and
Cellophane
The polyfunctional reactivity of glycerol is used
in the production of phthalic and maleic alkyd
resins (→ Alkyd Resins) and in cross-linked
polyesters from mono- and dicarboxylic acids
and polyols. Polyether polyols made of glyc-
erol in combination with propylene- and ethyl-
ene oxide are polymerized with diisocyanates in
the presence of highly volatile solvents to form
flexible or rigid polyurethane foams. Glycerol
also serves as a moisturizer and plasticiz er in
cellulose films.
9.3. Use in Tobacco Industry
Glycerol is in use as a solvent for flavor compo-
sitions for tobacco. It also serves as a humidifier
and plasticizer for the tobacco. Glycerol triac-
etate (triacetin) is used as a softener for cigarette
filters.
9.4. Other Applications
Glycerol is used as a hydraulic agent and in hy-
draulic fluid formulations. Technical esters of
glycerol with fatty acids are in use for synthetic
lubricants in the automotive industry and as lu-
bricants in the food industry. They are used for
readily and totally biodegradable loss lubrica-
tion, e.g., in the agriculture and forest industries.
Polyglycerols have a wide range of applications
as emulsifiers. Inks and printing colors contain
glycerol to prolong their servic life. The paper
industry uses glycerol a s a humidifier, plasti-
cizer, and lubricant.
9.5. Future Applications
tert-Butyl ethers of glycerol have mainly been
studied for fuel applications. The octane num-
bers for the ether product mixture are 112-128
(BRON) and 91-99 (BMON) [65] and these val-
ues indicate that in this sense they are suitable
to be used as gasoline components. However,
these products are not yet in commercial pro-
duction, but other ethers resembling their struc-
ture, such as MTBE (methyl-tert-butyl ether)
and ETBE (ethyl-tert-butyl ether), are currently
used in gasoline as high -octane components.
The oxygen-containing components, i.e., oxy-
genates have been observed to enhance the burn-
ing of the fuel resulting in cleaner burning and
less-harmful exhaust gases.
The ethers are mainly studied for the gasoline
applications but it has also been suggested that
they could be used as biodiesel additive [66]. The
addition of the ethers in the biodiesel decreases
the viscosity, cloud point, and pour point which
enables the fuel to be used in lower tempera-
ture. Thus the properties of biodiesel are brought
closer to conventional diesel fuel.
10. Economic Aspects
Estimated worldwide consumption of glycerol
amounts to ca. 750 000 t/a; about 65 % of the to-
tal production is in Europe and the United States.
Annual production (103 t) is shown in Figure 16.
The fraction of synthetic glycerol is ca. 10 %.
The price of glycerol is subject to fluctuation.
In times of higher prices, glycerol is partly re-
placed in certain applications by products such
as glycols or sorbitol. Nevertheless, the con-
sumption of glycerol increased from 550 000 t
to 750 000 t from 1986 to 1998 corresponding
to an increase of ca. 3 % per year.
As glycerol is a byproduct in many processes
its production rate is not dependent on the mar-
ket demand. Since 1995 there has been over-
supply of glycerol in the world market and the
increasing production of biodiesel increases the
oversupply further. It has been estimated that by

the year 2020 the production is six times more
than the demand.
Figure 16. Annual production of glycerol (worldwide)
11. Toxicology
Glycerol is not harmful to health. Oral doses
have a demulcent and mildly laxative effect. In-
gestion of large amounts may produce headache,
thirst, nausea, and hyperglycemia. Slight irrita-
tion of the skin or mucous membranes is possi-
ble on contact with undiluted glycerol because
the strongly hygroscopic glycerol absorbs water
from the skin.
There is no glycerol-specific aerosol limit.
However, in UK and USA the recommended
general long-term (8-hour TWA) exposure limit
for aerosols is 10 mg/m3 and has also to be ob-
served for glycerol mists.
12. References
1. M. Heming, “Glycerin Market Report”,
January 1999, CTVO-Networkshop.
2. S. Claude, Fett/Lipid 101 (1999) 101 – 104.
3. D. F. Stedmann, Trans. Faraday Soc. 24
(1928) 289 – 298.
Glycerol 15
4. I. C. Chu, S. L. Wang, S. L. Levy, R. Paul:
Vapor Liquid Equilibrium Data, I. W.
Edwards, Michigan 1956.
5. N. M. Sokulov, L. N. Tsygankova, N. M.
Zhavornokov, Khim. Promst. (Moscow) 48
(1972) 96;
Chem. Abstr. 76 (1972) 154 052 z.
6. R. C. Reid, I. M. Prausnitz, T. K. Sherwood:
The Properties of Gases and Liquids, 3rd ed.,
McGraw-Hill, New York 1977;
VDI Wärmeatlas, 8th ed., VDI Verlag GmbH,
Düsseldorf 1997/98.
7. C. S. Miner, N. N. Dalton: Glycerol, Reinhold
Pub. Corp., New York 1953.
8. L. H. Horsley, Ind. Eng. Chem., Anal. Ed., 19
(1947) 508 – 609.
9. A. Hammel, Z. Physik. Chem. 90 (1915) 121 –
125.
10. Physical Properties of Glycerine and its
Solutions, Glycerine Producers Association,
New York 1963.
11. Chemical Properties and Derivatives of
Glycerine, Glycerine Producers Association,
New York 1965.
12. R. Garcia, M. Besson, P. Gallezot, Appl. Catal.
127 (1995) 165 – 167.
13. L. H. Ohrem, H. Vosss, Process Biochem. 31
(1996) 295.
14. E. Drent, W. W. Jäger, PCT Int. Appl. WO
99/05085, 4.2.99
15. A. P. Zeng, H. Biebl, W. D. Deckwer, ACS
Symp. Ser. 64 (1997) 666.
16. K. Urata, N. Takaishi, JAOCS 73 (1996) 819.
17. K. Urata, N. Takaishi, J. Surf. Det. 1 (1998) 73.
18. B. Gutsche, Fett/Lipid 99 (1997) 418 – 427.
19. D. R. Asher, D. W. Simpson, J. Phys. Chem.
60 (1956) 518 – 521.
20. P. Deckert, W. Arlt, Chem.-Ing.-Tech. 66
(1994) 1334 – 1340.
21. Glycerine recovery, Crown Iron Works
Company, Minneapolis (Minn.), U.S.A.
(company brochure ’96 and information ’99).
22. Am. Oil Chem. Soc.: “Short Course on Fatty
Acids”, Kings Island, Ohio, Sept. 13 – 16,
1987.
23. H. W. Keller, A. W. Michalson, A. D. Payne,
JAOCS 33 (1956) 435 – 437.
24. Glycerine, Buss SMS GmbH, Butzbach,
Federal Republic of Germany; Company
brochure.
25. EP 014 135 8531, 184 (R. Brockmann et al.).
26. Lewatit/Lewasorb, Bayer AG, Leverkusen
(FRG); Company brochure.
27. F. Martinola, Chem. Ing. Tech. 51 (1979) 728 –
736.
16 Glycerol
28. K. Terelak et al., Chem. Tech. (Leipzig) 33
(1981) 315 – 316.
29. Shell Dev. Co., US 2 605 293, 1952 (F. T.
Tymstra).
30. Shell Dev. Co., US 2 810 768, 1957 (K. B.
Cofer).
31. Pittsburgh Plate Glass Co., GB 926 804, 1963
(W. B. Graybill, H. J. Vogt, D. E. Wiley).
32. Shell Dev. Co., US 2 779 801, 1957 (H. D. V.
Finch, A. D. Benedictis).
33. Progil S. A., FR 1 271 563, 1962 (A. Thizy,
M. E. Degeorges, E. Charles).
34. P. Vijaikishore, N. G. Karanth, Process
Biochem. 21 (1986) no. 2, 54 – 57.
35. R. Fusheng, Xiandai Huagong 16 (1996) 36 –
40.
36. C. Compagno, F. Boschi, B. M. Ranzi,
Biocatal. Biotransform. 16 (1998) 135.
37. N. A. Mostafa, Y. H. Magdy, Energy Convers.
Manage. 39 (1998) 671.
38. Daicel Chem. Ind., JP 58 180 444, 1982 (J.
Goto).
39. Kao Corp., DE 3 533 615, 1986 (M. Tanigaki
et al.).
40. M. Bühler, Ch. Wandrey, Fat Science
Technology 89 (1987) 156 – 164; 598 – 605.
41. J. Hirano, Chem. Econ. Eng. Rev. 18 (1986) 9
– 13.
42. M. Avron, Adv. Photosynth. Res. Proc. Int.
Congr. Photosynth. 6th 1983, 745 – 753.
43. B. J. Chem., C. H. Chi, Biotechnol. Bioeng. 23
(1981) no. 6, 1267 – 1287.
44. R. Fonseca et al., High-Pressure Sci. Technol.
AIRAPT Conf. 6th 1977 1 (1979) 733 – 738.
45. B. L. Zhang et al., J. Agric. Food Chem. 46
(1998) 1374 – 1380.
46. B. L. Zhang et al., Anal. Chem. 71 (1999) 2301
– 2306.
47. Rechnender Digitaler Dichtemesser für
Flüssigkeiten und Gase (nach O. Kratky, H.
Leopold und H. Stabinger, Graz); Fa. Paar
K.G., A-8054 Graz–Austria.
48. DIN 17 440: Nichtrostender Stahl (July 1985).
49. American Society for Testing and Materials
(ASTM), no. A 167, Type 304; no. A 167,
Type 316.
50. A. A. Newman: Glycerol, Morgan-Grampian,
London 1968.
51. E. Schlenker: Das Glycerin, Wissenschaftliche
Verlagsgesellschaft, Stuttgart 1932.
52. H. Kimura, Appl. Catal. A, 105 (1993) 147.
53. R. Garcia, M. Besson, P. Gallezot, Appl. Catal.
A, 127 (1995) 165–176.
54. S. Carrettin, P. McMorn, P. Johnston, K.
Griffin, C. J. Kielyc and G. J. Hutchings, Phys.
Chem. Chem. Phys. 5 (2003) 1329–1336.
55. R. Ciriminna, M. Pagliaro, Adv. Synt. Catal.
345 (2003) 383–388.
56. A. Behr, L. Obendorf, Chemie Ingenieur
Technik 73 (2001) 1463–1467.
57. ARCO Chemical Technology L.P., US 5 476
971, 1995 (V. P. Gupta).
58. Fina Research S.A., EP 0649 829, 1995 (C.
Dewattines, H. Hinnekens).
59. Henkel KGAA, DE 4 222 183, 1994 (A. Behr,
H. Schmidke, C. Lohr, M. Schneider).
60. ARCO Chemical Technology, US 5 308 365,
1994 (H. S. Kesling, L. Karas, F. J. Liotta).
61. U. Steinbrenner, W. Preuss, Fat Science
Technology 89 (1987) 297 – 303.
62. 75 Years Henkel Glycerine, Henkel KGaA,
Düsseldorf 1986, company brochure.
63. E. Jungermann, N. O. V. Sonntag: Glycerine:
A Key Cosmetic Ingredient, Marcel Dekker
Inc., New York 1991.
64. The United Kingdom Glycerine Producers’
Assoc., London: Glycerine in pharmacy,
glycerine in cosmetics,
glycerine-miscellaneous uses.
65. R. Wessendorf, Erdöl Kohle Erdgas
Petrochem. 48 (1995) no. 3, 138–143.
66. University of Nebraska, US 6 015 440, 2001
(H. Noureddini).
 Glyoxal 1

Glyoxal
Georges Mattioda, Société Française Hoechst, C.R.A., Stains, France
Alain Blanc, Société Française Hoechst, C.R.A., Stains, France

1. Introduction . . . . . . . . . . . . . . . . . . 1 5. Uses . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Physical Properties . . . . . . . . . . . . . . 1
6. Toxicology and Occupational Health . . 4
3. Chemical Properties . . . . . . . . . . . . . 1
4. Production . . . . . . . . . . . . . . . . . . . 2 7. References . . . . . . . . . . . . . . . . . . . 4

1. Introduction polyglyoxal, which is infusible, depolymerizes

Glyoxal [107-22-2], ethanedial, diformyl,
C2 H2 O2 , M r 58.04, was first prepared in 1856
by Debus, through the controlled oxidation of
ethanol with nitric acid [1].
upon heating, and decomposes above 150 ◦ C.
In 40 % aqueous solution, glyoxal exists
mainly in the form of the hydrated monomer
(1), together with a dioxolane dimer (2) and two
bis(dioxolane) trimers (3); these components re-
present ca. 80 % of its total composition [3].

2. Physical Properties
Anhydrous glyoxal is a liquid at ambient tem-
perature; it crystallizes at 15 ◦ C in the form of
yellow prismatic crystals and boils at 50.4 ◦ C
(101.3 kPa), giving off green vapors with a pun-
gent odor. The liquid has a specific gravity of
1.14 at 20 ◦ C; n20.5
D = 1.3826. Electron diffrac- In concentrated aqueous solution the most
tion and infrared spectra show that the molecule
abundant component is the hydrated trimer (3),
is planar; the trans configuration is the more sta-
which is responsible for the cloudiness or crys-
ble [2].
talline precipitates in aqueous glyoxal solutions.
More highly condensed oligomers are also
present, as shown by 1 H and 13 C NMR during
acetalization by low molecular mass primary al-
cohols [4]; the species present have been quan-
tified as a function of concentration and temper-
ature.
3. Chemical Properties With alcohols, under acid catalysis, a mix-
ture of oligomeric acetals is obtained. Glycolates
As the simplest dialdehyde, glyoxal un-
are also formed; glycolate formation predomi-
dergoes reactions characteristic of aldehy-
nates in the presence of a strong acid [5]. Gly-
des (→Aldehydes, Aliphatic and Araliphatic,
oxal acetals and thioacetals are used as complex-
Chap. 2.2.).
forming agents [6].
Anhydrous monomeric glyoxal can be ob-
tained by heating polyglyoxal in the presence of
phosphorus pentoxide. Anhydrous glyoxal poly-
merizes rapidly under the action of traces of wa-
ter, forming a series of hydrated oligomers. Gly-
oxal is used only as an aqueous solution, at con-
centrations between 30 and 50 %. Evaporation
of this solution produces a white, solid mass of

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 491
2 Glyoxal
With primary amines glyoxal forms diimines,
reduction of which leads to ethylenediamines,
[7] which are used industrially to cross-link iso-
cyanates in coatings.
Glyoxal reacts with β-hydroxyalkylamines to
give a heterodecalin:
With diethanolamine [111-42-2], the final
product is N,N-bis(2-hydroxyethyl)glycine
[150-25-4] (R = −CH2 CH2 OH):
The latter is used to form com-
plexes with polyvalent cations (see also
→ Ethylenediaminetetraacetic Acid and Related
Chelating Agents) [8].
The corresponding aminoacetamides are
formed with secondary amines [9], [10]:
Controlled oxidation leads successively to
glyoxylic acid [298-12-4] and oxalic acid
[144-62-7] [11], [12].
With aldehydes and enolizable ketones, gly-
oxal leads to the expected aldol condensation
products [13]; e.g., with acetone or isobutyr-
aldehyde:
With amides and urethanes, di- and
tetramides are obtained, depending on the pH
[14], [15].
In alkaline medium, glyoxal disproportion-
ates by an internal Cannizzaro reaction to the
glycolate [16–18]:
4. Production
Among the numerous processes for produc-
ing glyoxal, only those using acetaldehyde
[75-07-0] and ethylene glycol [107-21-1] as
starting materials have been developed commer-
cially.
From Acetaldehyde. Oxidation with nitric
acid was examined by Ljubowin as early as
1875 and patented in 1942 [19]. Reaction takes
place at ca. 40 ◦ C and is carried out industrially
as a continuous process. Maximum yield is ca.
70 %; selectivity is a function of the relative con-
centrations of reagents. After the removal of ex-
 Glyoxal 3

cess acetaldehyde, the glyoxal formed, which is
contaminated with acetic, formic, and glyoxylic
acids, is purified by passage of the aqueous solu-
tion through an ion-exchange resin. The solution
is then concentrated to a glyoxal content of about
40 %.
Selenium oxide [7446-08-4] is more selec-
tive than nitric acid, and the yield is ca. 84 %;
the selenium can be recycled by oxidation with
hydrogen peroxide [20]. This process has not
been carried out on an industrial scale.
The dual functionality and the ability of
glyoxal to form heterocyclic compounds have
been used in the production of resins for im-
parting crease resistance to textiles. The re-
action proceeds through the intermediate for-
mation of 4,5-dihydroxy-2-imidazolidinone (4)
[3720-97-6] (DHEU) and its methylolated
derivatives (DMDHEU).

From Ethylene Glycol. The gas-phase oxi-

dation of ethylene glycol by atmospheric oxy-
gen in the presence of dehydrogenation catalysts
(metallic copper or silver) represents the basis
of the Laporte process [21] and has been used
in several industrial production processes. Reac- Ethers of DMDHEU are among the most effec-
tion occurs between 400 and 600 ◦ C; the yield tive resins for the crease-resistant treatment of
is 70 – 80 %. The main impurity is formaldehyde cotton-based fabrics [27], [28].
[50-00-0], whose subsequent separation is diffi- The reducing properties of glyoxal are used
cult. This reaction has also been carried out in in the photographic industry and in glassmaking
the liquid phase and under irradiation. for the production of silvered glass mirrors.
Glyoxal bisulfite (available as the monohy-
Other Processes. Ethylene can be oxidized
drate) is used as a resist agent in printing with
by aqueous nitric acid in the presence of pal-
reactive dyes and as a leveling agent in dyeing
ladium [22], by atmospheric oxygen, or by se-
polyamide with acid dyes.
lenium oxide deposited on silica [23]. Glyoxal
An important class of molecules used as
may also be formed by oxidation of acetylene
cross-linking agents is obtained by nucleophilic
[24] or benzene [25] with ozone. Ethylene oxide
substitution of glyoxal. Examples include the
has been proposed as a substrate for oxidation.
bisacrylamide (5) [76843-24-8] and the tetraal-
Although oxalic acid and its derivatives can be
lylacetal (6) [16646-44-9].
reduced to glyoxal, these processes have not
been developed further.

5. Uses
Glyoxal is supplied mainly as a 40 % aqueous
solution. Various polyhydroxy polymers (e.g.,
starch or poly(vinyl alcohol)) can be used to sta-
bilize glyoxal.
The bifunctionality of glyoxal has been used
to cross-link functionalized macromolecules
such as cellulose, polyacrylamides, poly(vinyl
alcohol), keratin, and other polycondensates.
For example, glyoxal is used as a cross-linking
agent for imparting wet strength to coated pa-
per. With cellulose, unstable hemiacetals are ob-
tained in the cold, which irreversibly form ac-
etals when heated in the presence of acid cata-
lysts [26].
Glyoxalbisacrylamide is used for the func-
tionalization of ion-exchange resins and in lat-
ices for treating textiles. Tetraallyloxyethane is
used as a cross-linking agent for polyacrylates
(→Polyacrylates) and for pressure-sensitive ad-
hesives.
Glyoxal is used in the fine chemicals in-
dustry for the production of various hete-
rocyclic compounds including tetraacetylgly-
4 Glyoxal
coluril [10543-60-9] (7) (a perborate ac-
celerator), imidazoles such as metronida-
zole [443-48-1] (8) that are effective against
anaerobic bacteria, and the pyrazine deriva-
tives sulfapyrazine [116-44-9] (9), thionazine
[297-97-2] (10), and pyrazinamide [98-96-4]
(11).
Glyoxal has bactericidal properties compara-
ble with those of glutaraldehyde and is used as
a disinfectant.
6. Toxicology and Occupational
Health
Glyoxal has low toxicity. The LD50 is
3300 mg/kg (oral, rat). No mortality was ob-
served in rats at a dosage of 1.3 mg/L inhaled
in a saturated atmosphere or with aerosols. Gly-
oxal was well tolerated topically in a rabbit skin
test but was irritating to the eyes. Glyoxal causes
an allergic sensitization in guinea pigs.
Glyoxal gives a positive result in the Ames
mutagenesis test, but it does not change cells in
the cell transformation test and has no elasto-
genic effect in the micronucleus test; it is also
not mutagenic in the Chinese hamster lung test.
All of these tests are generally positive with sub-
stances known to be mutagenic.
7. References
1. H. Debus, Ann. Chem. Pharm. 100 (1856) 5;
102 (1857) 20 – 24.
2. U. Pincelli, B. Cadioli, D. J. David, J. Mol.
Struct. 12 (1971) 171.
3. E. B. Whipple, J. Am. Chem. Soc. 92 (1970)
7183 – 7186.
4. F. Chastrette, C. Bracoud, M. Chastrette, G.
Mattioda, Y. Christidis, Bull. Soc. Chim. Fr.
1983 33 – 40.
5. J. M. Kliegman, R. K. Barnes, J. Org. Chem.
38 (1973) 556 – 560; J. Org. Chem. 39 (1974)
1772 – 1776.
6. F. Chastrette, M. Hassamblay, M. Chastrette,
Bull. Soc. Chim. Fr. 1976, 601 – 606;607 – 612;
613 – 615.
7. Hoechst, DE 2 938 710, 1979 (H. Diery, W.
Wagemann).
8. A. Le Rouzic, D. Raphalen, D. Papillon, M.
Kerfanto, Tetrahedron Lett. 26 (1985)
1853 – 1856;Société Française Hoechst,
FR 2 561 645, 1984 (A. Blanc); FR 2 561 648,
1984 (A. Blanc).
9. K. Maurer, E. H. Woltersdord, Z. Physiol.
Chem. 254 (1938) 18 – 24.
10. P. Ferruti, A. Feré, L. Zetta, A. Bettelli, J.
Chem. Soc. C. 1971, 2984 – 2985.
11. BASF, DE 932 369, 1955 (H. Spänig, G.
Triem).
12. Nobel Bozel, FR 1 326 605, 1962 (L. Gandon).
13. BASF, DE 2 003 600, 1970 (F. Merger).
14. S. L. Vail, C. M. Moran, R. H. Barker, J. Org.
Chem. 30 (1965) 1195 – 1199.
15. S. L. Vail, A. G. Pierce, J. Org. Chem. 37
(1972) 391 – 393.
16. P. Salomaa, Acta. Chem. Scand. 10 (1956)
311 – 319.
17. C. L. Arcus, B. A. Jackson, Chem. Ind.
(London) 1964, 2022 – 2023.
18. A. R. Fratzke, P. J. Reilly, Int. J. Chem. Kinet.
18 (1986) no. 7, 757 – 773.
19. I. G. Farbenindustrie AG, BF 885 931 (1942).
20. Air Liquide, FR 2 038 575, 1969 (J. P.
Zumbrunn).
21. Laporte Chemicals, GB 1 272 592, 1963
(B. K. Howe, F. R. Hary, D. A. Clarke).
22. BASF, DE 1 166 173, 1962 (R. Platz, W.
Fuchs); DE 1 231 230, 1964 (R. Platz, H.
Nohe).
23. E. Costa Novella, Ann. Quim. 68 (1972) no. 3,
325 – 332;Chem. Abstr., 77, 113 760 f.
24. Imperial Chemical Industries, GB 1 071 902,
1965 (R. A. Rennie).
25. Inmont Corp., US 3 637 860, 1968 (W. P.
Keaveney, J. J. Pappas).
26. F. S. H. Head, J. Text. Inst. 49 (1958)
T 345 – T 356.
27. H. Petersen, Text. Res. J. (1958) 156 – 176.
28. S. L. Vail, G. B. Verburg, A. H. Young, Text.
Res. J. (1969) 86 – 93.

Glyoxylic Acid
Georges Mattioda, Société Française Hoechst, C.R.A., Stains, France
Yani Christidis, Société Française Hoechst, C.R.A., Stains, France
1. Introduction . . . . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . . . . .
3. Chemical Properties . . . . . . . . . . . . .
1. Introduction
Glyoxylic acid [298-12-4], oxoacetic acid, gly-
oxalic acid, OHC−COOH, M r 74.04, is the sim-
plest α-oxocarboxylic acid. It is found in plants
and is involved in the metabolic cycle of ani-
mals. Glyoxylic acid was discovered by Debus,
who established its formula in 1856 [1]. This
formula was described more precisely as that of
the monohydrate by Perkin in 1868 [2].
In 1957, Kronberg and Krebs established
the basis of the metabolic cycle of glyoxylic acid
[3], in which isocitrate is converted to malate
anaerobically. This cycle acts as a relay in the
tricarboxylic acid cycle under specific condi-
tions of plant life, such as germination or in-
effective photosynthesis [4], [5].
2. Physical Properties
Glyoxylic acid crystallizes as the monohydrate
upon controlled concentration of its aqueous
solution. When dry, the monohydrate has mp
52 – 53 ◦ C. The dissociation constant in aque-
ous solution is 4.7×10−4 , and the specific heat
is 1.80 kJ kg−1 K−1 . The density of a 50 % aque-
ous solution of the acid, the only commercial
form, is 1.34 g/cm3 at 20 ◦ C; the refractive in-
dex (20 ◦ C) is 1.416.
The use of NMR spectroscopy (1 H [6] and
13
C [7]) has confirmed the existence of glyoxylic
acid in aqueous solution as the dihydroxy acid
(1) together with a small proportion of the linear
dimer (2).

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a12 495
Glyoxylic Acid 1
1 4. Production . . . . . . . . . . . . . . . . . . . 3
1 5. Toxicology . . . . . . . . . . . . . . . . . . . 3
1 6. References . . . . . . . . . . . . . . . . . . . 3
Glyoxylic acid is strongly hydrophilic; it is
soluble in alcohols, with which it reacts, and in
water-miscible solvents; it has a very low solu-
bility in ether and other organic solvents.
Glyoxylic acid forms complexes with ions of
alkali and alkaline-earth metals; it has a chelat-
ing power of 30 mg of calcium carbonate per
gram of 50 % aqueous solution.
3. Chemical Properties
Glyoxylic acid contains two functional groups:
the carbonyl group, which undergoes reac-
tions characteristic of aldehydes (→Aldehydes,
Aliphatic and Araliphatic, Chap. 2.2.), and the
carboxylic acid group (→Carboxylic Acids,
Aliphatic, Chap. 3.). The aldehyde group re-
acts readily with nucleophilic reagents; the hy-
drated aldehyde and the hemiacetal react simi-
larly. With ambident nucleophiles, the carboxyl-
ic group may also react, leading to intramolec-
ular ring formation. Various heterocyclic com-
pounds can be obtained by coupling polynu-
cleophiles with glyoxylic acid: o-phenylene-
diamine [95-54-5] gives 2-hydroxyquinoxaline
[1196-57-2] (3); with urea [57-13-6] and an acid
catalyst, allantoin [97-59-6] (4) is obtained in
60 % yield [8].
2 Glyoxylic Acid

On heating, glyoxylic acid disproportionates

to a mixture of glycolic acid [79-14-1] and ox-
alic acid [144-62-7]; glyoxylic acid is also easily
oxidized to oxalic acid by nitric acid.

The reaction with phenols is used in sev-

eral industrial syntheses of benzaldehydes.
For example, guaiacol [90-05-1] is converted
Reactions that have been used industrially to vanillin [121-33-5] by oxidative decarbox-
include the Mannich reaction and amidoalkyl- ylation of the corresponding mandelic acid [13].
ation. Thus, with phenol and ethylenediamine
in alkaline medium, glyoxylic acid leads to the
sodium salt of N,N -ethylenebis[2-(2-hydroxy-
phenyl)glycine] (EHPG, 5), which forms com-
plexes with iron (III) [9].

The mandelic acid intermediate may be mod-

ified further: reaction of phenol and glyoxylic
acid in the presence of a reducing agent such as
phosphorus – iodine leads directly to hydroxy-
phenylacetic acid [14], a building block for phar-
maceuticals such as Atenolol.
Glyoxylic acid, phenol, and ammonia react
to give 4-hydroxyphenylglycine, an intermedi-
ate for the semisynthetic penicillin amoxicillin
[10] (see →Antibiotics).

With thiophene, this reaction yields 2-

At slightly alkaline pH, glyoxylic acid reacts
with amides such as acrylamide [79-06-1] to
form acrylamidoglycolic acid (AGA), which is
used as a copolymerizable cross-linking agent
[11] (→Polyacrylamides and Poly(Acrylic
Acids)).
thienylacetic acid, which is used to prepare the
semisynthetic cephalosporins cephalothin and
cefoxitin.
Glyoxylic acid and hydrochloric acid can
be used to chloroalkylate aromatic compounds
[15].
Glyoxylic acid undergoes the aldol reaction;
the corresponding benzoylacrylic acids are ob-
tained with acetophenones [16]:

Several derivatives of AGA have found indus-

trial application; e.g., the methyl ether ester is
used in coatings and paint for automobiles.
Glyoxylic acid is treated with Wittig ylides
Glyoxylic acid combines with phenol in al-
to form carboxyl functional polyenes of the vi-
kaline medium to give 4-hydroxymandelic acid
tamin A type [17].
with good selectivity [12].

Esters of glyoxylic acid, obtained by dehy-
drative distillation of the hemiacetal esters in
the presence of phosphorus pentoxide, can be
polymerized under the action of a base. After
saponification, the resulting polymers show use-
ful chelating properties with the advantage of
good biodegradability [18], [19]. Low molecu-
lar mass polyglyoxylates have been proposed as
substitutes for sodium tripolyphosphates (TPP)
in detergents to control water hardness.
4. Production
Glyoxylic acid is produced industrially by oxi-
dation of glyoxal in aqueous solution with 65 %
nitric acid in mole ratios of 1 : 1 to 1 : 1.5 bet-
ween 40 and 90 ◦ C. The main byproduct of this
process is oxalic acid, which is separated by low-
temperature crystallization. The solution is then
purified by passage through an anion-exchange
resin or by electrodialysis, which removes the
residual nitric acid.
Glyoxal can also be oxidized at the anode of
a two-compartment electrolytic cell in the pres-
ence of chloride ion [20]. Glyoxylic acid may be
synthesized by catalytic oxidation of ethylene or
Glyoxylic Acid 3
acetaldehyde, but the selectivity is low and these
routes have not been used industrially.
The cathodic reduction of oxalic acid gives a
very good chemical yield (85 %), but this tech-
nique encounters problems with passivation of
the lead electrodes [21], [22].
Another method is oxidative cleavage of
maleic acid or its esters by ozone. This process,
has been adapted to the preparation of hemiac-
etal esters [23].
5. Toxicology
The LD50 is 2500 mg/kg (oral, rat). Glyoxylic
acid is corrosive to the eye (rabbit), does not
irritate the skin, but causes an allergic sensiti-
zation in guinea pigs. No mutagenic effect was
found in the Ames mutagenicity test; glyoxylic
acid is completely inactive in the so-called mi-
cronucleus mutagenicity test in mice.
Glyoxylic acid is a metabolite in mammalian
biochemical pathways.
6. References
1. H. Debus, Ann. Chem. Pharm. 100 (1856) 1.
2. W. H. Perkin, B. F. Duffa, Bull. Soc. Chim. Fr.
10 (1868) 213.
3. H. L. Kornberg, H. A. Krebs, Nature (London)
179 (1957) 988 – 991.
4. H. Beevers, Ann. N.Y. Acad. Sci. 168 (1969)
313 – 324.
5. M. Cioni et al., Comp. Biochem. Physiol. 70 B
(1981) 1 – 26.
6. G. Ojelund, I. Wadso, Acta Chem. Scand. 21
(1967) no. 6, 1408 – 1414.
7. F. Chastrette, C. Bracoud, Bull. Soc. Chim. Fr.
1985 (II) 66 – 74.
8. BASF, DE-OS 1 939 924, 1969 (W. Mesch,
O. A. Grosskinsky, N. Lösch).
9. Ciba-Geigy, US 4 130 582, 1977 (H. E. Petree,
H. Myatt, A. M. Jelenevsky).
10. Beecham, GB 978 178, 1962 (J. H. C. Nayler,
H. Smith).
11. Nobel Bozel, FR 1 411 715, 1964.
12. Soc. Française Hoechst, FR 2 440 350, 1978
(A. Schouteeten, Y. Christidis).
13. Haarmann & Reimer, DE-OS 2 115 551, 1971
(K. Bauer, W. Steuer).
14. Soc. Française Hoechst, FR 2 470 127, 1979
(J. C. Vallejos, Y. Christidis).
4 Glyoxylic Acid
15. Soc. Française Hoechst, FR 2 376 112, 1976
(E. Herman, H. Diery, M. Soreau, Y.
Christidis).
16. Roussel-Uclaf, FR 2 504 005, 1981 (Y.
Christidis, R. Fournex, C. Tournemine).
17. Hoffmann La Roche, US 4 224 244, 1980 (W.
Bollag, R. Ruegg, G. Ryser).
18. Monsanto, US 4 144 226, 1977 (M. M.
Crutchfield, V. D. Papanu, C. B. Warren).
19. Procter & Gamble, US 4 284 524, 1980 (L. A.
Gilbert).
Glyptals → Alkyd Resins
20. Chlorine Engineers and Daicel Chem.,
FR 2 443 517, 1979 (H. Harada, K. Hirao, M.
Ichino, T. Mitani).
21. I. V. Kudryashov et al., Tr. Mosk. Khim.
Tekhnol. Inst. 49 (1965) 111 – 115; Chem.
Abstr. 65 3328 d.
22. K. Scott, Chem. Eng. Res. Des. 64 (1986)
no. 4, 266 – 272.
23. Lentia, DE 3 224 795, 1982 (A. Sajtos, M.
Wechsberg, E. Roithner).
 Gold, Gold Alloys, and Gold Compounds 1

Gold, Gold Alloys, and Gold Compounds

Hermann Renner, Degussa AG (retired), Hanau, Federal Republic of Germany (Chaps. 1 – 3, Sections 4.1,
4.2, Chap. 11)
Günther Schlamp, Demetron GmbH (retired), Hanau, Federal Republic of Germany (Section 2.1, Chap. 8,
Sections 10.3.1, 10.3.2, 10.4 – 10.10)
Dieter Hollmann, dmc2 Degussa Metals, Catalysts AG, Frankfurt, Federal Republic of Germany
(Chaps. 5 – 7)
Hans Martin Lüschow, Degussa-Hüls AG (retired), Hanau, Federal Republic of Germany (Chap. 9)
Peter Tews, Allgem. Gold und Silberscheideanstalt (AGOSI), Pforzheim, Federal Republic of Germany
(Sections 10.1, 10.2)
Josef Rothaut, Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of Germany (Section 10.7)
Klaus Dermann, Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of Germany (Section 10.7)
Alfons Knödler, Forschungsinstitut für Edelmetalle und Metallchemie (retired), Schwäbisch Gmünd,
Federal Republic of Germany (Section 10.8.1)
Christian Hecht, dmc2 Degussa Metals, Catalysts AG, Frankfurt, Federal Republic of Germany
(Section 10.8.2)
Martin Schlott, Leybold Materials, Hanau, Federal Republic of Germany (Section 10.8.3)
Ralf Drieselmann, dmc2 Degussa Metals, Catalysts AG, Frankfurt, Federal Republic of Germany (Chap. 11)
Catrin Peter, Klinikum der Friedrich-Schiller-Universität, Jena, Federal Republic of Germany (Chap. 12)
Rainer Schiele, Klinikum der Friedrich-Schiller-Universität, Jena, Federal Republic of Germany (Chap. 12)

1. History . . . . . . . . . . . . . . . . . . 3 6. Recovery of Gold from Secondary

1.1. Centers of Gold Production . . . . 3 Materials . . . . . . . . . . . . . . . . . 17
1.2. Production . . . . . . . . . . . . . . . . 5 6.1. Recovery from Gold Alloys . . . . . 17
1.3. Development of Production Pro- 6.2. Recovery from Sweeps . . . . . . . . 18
cesses . . . . . . . . . . . . . . . . . . . 5 6.3. Recovery from Surface-Coated
2. Properties . . . . . . . . . . . . . . . . 6 Materials . . . . . . . . . . . . . . . . . 18
2.1. Physical Properties . . . . . . . . . . 6 7. Gold Compounds . . . . . . . . . . . 19
2.2. Chemical Properties . . . . . . . . . 7 7.1. Potassium Dicyanoaurate(I) . . . . 19
3. Occurrence . . . . . . . . . . . . . . . 8 7.2. Tetrachloroauric(III) Acid . . . . . 21
3.1. Abundance . . . . . . . . . . . . . . . 8 7.3. Sodium Disulfitoaurate(I) . . . . . . 21
3.2. Gold Deposits . . . . . . . . . . . . . . 8 7.4. Miscellaneous Gold Compounds . 22
8. Gold Alloys . . . . . . . . . . . . . . . 22
3.3. Gold Reserves and Resources . . . 9
8.1. Binary Alloys . . . . . . . . . . . . . . 24
4. Production . . . . . . . . . . . . . . . . 9
8.2. Ternary Alloys . . . . . . . . . . . . . 29
4.1. Ore Treatment . . . . . . . . . . . . . 9
8.3. Higher Alloys . . . . . . . . . . . . . . 31
4.2. Cyanidation . . . . . . . . . . . . . . . 10 8.4. Production and Processing . . . . . 31
4.3. Recovery of Gold with Carbon . . 11 9. Quality Specifications and Analysis 33
4.3.1. Adsorption of Gold by Carbon . . . . 11 9.1. Quality Specifications . . . . . . . . 33
4.3.2. Carbon-in-Pulp Process . . . . . . . . 12 9.2. Sampling . . . . . . . . . . . . . . . . . 33
4.3.3. Carbon-in-Leach Process . . . . . . . 14 9.3. Qualitative and Semiquantitative
5. Gold Refining . . . . . . . . . . . . . . 14 Analysis . . . . . . . . . . . . . . . . . 33
5.1. Chemical Refining . . . . . . . . . . 14 9.4. Quantitative Analysis . . . . . . . . 34
5.2. Miller Process . . . . . . . . . . . . . 15 9.5. Purity Analysis . . . . . . . . . . . . . 35
5.3. Wohlwill Electrolysis . . . . . . . . . 16 9.5.1. Direct Analysis of Metallic Gold . . 35
5.4. Solvent Extraction . . . . . . . . . . 17 9.5.2. Purity of Gold Solution . . . . . . . . 36

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 499
2 Gold, Gold Alloys, and Gold Compounds
9.6. Trace Analysis . . . . . . . . . . . . .
10. Uses of Gold and Gold Alloys . . .
10.1. Coins, Medals, and Bars . . . . . .
10.2. Jewelry . . . . . . . . . . . . . . . . . .
10.3. Electronics and Electrical Engi-
neering . . . . . . . . . . . . . . . . . .
10.3.1. Electronics . . . . . . . . . . . . . . . .
10.3.2. Electrical Engineering . . . . . . . . .
10.4. Solders . . . . . . . . . . . . . . . . . .
10.5. Pen Nibs . . . . . . . . . . . . . . . . .
10.6. Chemical Technology . . . . . . . . .
1. History [1–24]
1.1. Centers of Gold Production
Gold is the first element that humans recognized
as a metal. Towards the end of the Middle Stone
Age and the onset of the Neolithic Age (ca.
8000 b.c.), the world’s climate changed greatly.
Large areas became arid, necessitating the es-
tablishment of permanent settlements in river
valleys such as the Euphrates, the Tigris, and
the Nile. The earliest archeological findings that
can be reliably dated were made in predynastic
Egypt (ca. 4000 b.c.) and Mesopotamia, which
the Sumerians settled in 3000 b.c. Outstanding
finds (ca. 3000 b.c.) were made close to modern
Varna, on the Bulgarian shores of the Black Sea.
Gold was first mentioned in literature in the In-
dian Vedanta (before 1000 b.c.), the writings of
Herodotus (484 – 425 b.c.), and the Old Testa-
ment (1000 b.c.).
The historical development of gold process-
ing and important gold production centers are
summarized in Figure 1. Egypt was the principal
gold country in the pre-Christian era and main-
tained that status until ca. 1500 b.c. Gold pro-
duction reached its peak about 1300 b.c. when
the first legal foundations for the production of
gold were laid, awarding the Pharaoh the abso-
lute monopoly. In ca. 2700 b.c. gold rings were
introduced as means of payment; the first gold
coins appeared around 600 b.c.
The origin of the gold used by the Egyptians
is unclear. Substantial portions appear to have
come from Nubia in Upper Egypt (nub = gold),
but considerable quantities were probably im-
ported following the frequently mentioned ex-
peditions to “Punt.”
36 10.7. Dental Materials . . . . . . . . . . . . 43
36 10.8. Coatings . . . . . . . . . . . . . . . . . 43
36 10.8.1. Electroplating and Electroforming . 43
37 10.8.2. Bright Gold . . . . . . . . . . . . . . . 44
10.8.3. Other Gold Coatings . . . . . . . . . . 46
39 10.9. Gold Leaf . . . . . . . . . . . . . . . . 46
39 10.10. Catalysts . . . . . . . . . . . . . . . . . 46
42 11. Economic Aspects . . . . . . . . . . . 47
42 12. Toxicology and Occupational
43 Health . . . . . . . . . . . . . . . . . . 48
43 13. References . . . . . . . . . . . . . . . . 49
The special status enjoyed by gold in Egypt
also exerted an influence in neighboring coun-
tries. The country of Ophir mentioned by
Solomon as the origin of his gold may be iden-
tical with Punt, but India may also have been
the supplier. The Egyptian gold trade expanded
particularly under the impetus of the seafaring
Phoenicians and Greeks.
Although Egypt was the principal gold coun-
try until about 1 b.c., gold was also found and
utilized in other regions including India, Ireland,
Bohemia, the Carpathian Mountains, Gaul, on
the Iberian peninsula, and in the Caucasus.
Even in ancient times the ownership of gold
shifted from one ruler to the other through con-
quests and the collection of tributes. Alexander
the Great obtained possession of Indian gold as
well as considerable portions of the Pharaohs’
treasure. The Romans had little of the metal in
their own regions but their military expeditions
netted them major amounts in the form of booty;
they also exploited the mineral wealth of the
countries they had conquered, especially Spain,
where up to 40 000 slaves were employed in min-
ing. The state’s accumulation of gold bars and
coins was immense. Later, however, more and
more gold was used in luxury goods and towards
the end of the Roman empire a gold shortage was
experienced.
In the region corresponding to modern-day
Zimbabwe, organized gold production existed
prior to 1000 a.d.
The advent of Christianity in the Middle Ages
reduced the general striving for gold. Moreover,
until the beginning of the Middle Ages no domi-
nant political power existed for organizing large-
scale gold production. In Europe, only the de-
posits in the Sudeten mountains, the Carpathi-
ans, and the Alps were of any significance. Out-
 Gold, Gold Alloys, and Gold Compounds 3

Figure 1. Historical survey of important gold production centers and gold processing techniques

side Europe, gold was produced in India, Japan,
and Siberia.
Following the discovery of America and the
rapid conquest of the New World at the end of the
fifteenth century, the Spaniards transferred con-
siderable amounts of gold from the New World
to Europe. Although the conquistadors found
a highly developed mining industry in Central
America, their efforts to increase gold produc-
tion were largely unsuccessful; most of the finds
consisted of silver. It was not until the discovery
of deposits in Brazil that there was a noticeable
4 Gold, Gold Alloys, and Gold Compounds
increase in world gold production. These de-
posits were exploited from 1725 to about 1800.
Since about 1750 gold has been mined on a
major scale on the eastern slopes of the Ural
mountains. In 1840, alluvial gold was disco-
vered in Siberia. The Russian deposits were ex-
ploited by the Czars and the land owners, who
had to pay their taxes in gold. Russia produced
about one fifth of the world’s gold production, a
proportion maintained until the present day.
The discovery of gold in California in 1848
increased gold production greatly. The special
laws issued in the Western parts of the United
States allowed private mining thanks to the right
to stake claims. This type of working continued
when gold deposits were found in Eastern Aus-
tralia (1851), Nevada (1859), Colorado (1875),
Alaska (1886), New Zealand and Western Aus-
tralia (1892), and Western Canada (1896). How-
ever, these deposits soon lost much of their im-
portance.
The strongest impetus was given to gold
production through the discovery of the gold-
fields of the Witwatersrand in South Africa in
1885. This extremely rich deposit appeared to
guarantee steady exploitation far into the fu-
ture. South African gold soon occupied a com-
manding position in the world market. Produc-
tion grew continuously except for a short in-
terruption by the Boer War (1899 – 1902). In
the 1970s, gold production largely stabilized in
South Africa and in the rest of the world. In
South Africa, several hundred thousand people
are now employed in the production of gold.
The discovery of large deposits of gold in
Brazil in the 1970s stimulated prospecting ac-
tivities. New production centers have been es-
tablished in the Sierra Pelada of Brazil, Canada,
Venezuela, New Guinea (Ok Tedi), and espe-
cially Western Australia, causing a pronounced
shift in the geographic distribution of world gold
production.
Gold mining in Ghana (Gold Coast) only be-
gan to play a role, if a modest one, in the twenti-
eth century, although the deposits were already
known in the Middle Ages. Gold production in
Zimbabwe and the neighboring eastern part of
the South African bush veld today form a mod-
erate but not insignificant part in the overall pro-
duction of southern Africa.
1.2. Production
Total gold production in antiquity can only be
assessed approximately. Up to the fall of the Ro-
man Empire, production may have amounted to
10 000 t.
A total production figure of 2000 – 3000 t has
been quoted for the Middle Ages. By the time
of the discovery of America, annual world pro-
duction had reached about 5 t.
An annual production of ca. 10 t was reached
in ca. 1700, rising to ca. 15 t in 1800 and to
40 t by 1848, the year the Californian deposits
were discovered. As early as 1852, more than
200 t/a were mined, but production subsequently
decreased until 1890. Thereafter, the increased
output of the South African mines raised an-
nual world production to 500 t in 1904, 700 t in
1907, and 1000 t in 1936. Since then, world an-
nual production, which was at times subject to
major fluctuations, has risen to over 2000 t. A
further 300 t/a result from industrial recycling.
The total world production of gold in 1991
exceeds 1.09 105 t [187]. More than a third of the
present-day gold inventory is held by the central
banks of the Western industrialized nations as
currency backing. An even larger proportion is
in private hands, much of it in the form of jew-
elry. Krugerrands alone accounted for 2000 t in
1967 – 1985, and smaller quantities are circulat-
ing in industry.
The shares of individual states in the over-
all production until now are divided among the
Republic of South Africa (40 %), the United
States (15 %), the ancient empires (ca. 10 %),
Russia/CIS (ca. 10 %), Australia and the Pacific
Region (ca. 10 %), and Canada (ca. 5 %).
1.3. Development of Production
Processes [25–27]
The development of gold production processes
is summarized in Figure 1. In antiquity, gold
grains obtained by washing river sands were
cold-worked into the desired objects. From ca.
3900 b.c., alluvial gold could be fused into larger
lumps. The ancient Egyptians were the first to
quarry gold-bearing rocks. Comminution of the
rocks and washing were often preceded by heat
treatment.
 Gold, Gold Alloys, and Gold Compounds
Analyses of archeological finds show that,
in Egypt, the separation of gold from silver
and copper was feasible, possibly as early as
2000 b.c. Silver was removed by annealing with
common salt to give silver chloride [8]. The
naturally occurring gold – silver alloy, electrum
magicum, was separated into its constituents.
The slagging of copper by adding lead followed
by cupellation was also known.
In Spain, the Romans developed the tech-
nique of flush mining, by which vast masses of
rock were dropped from a height, comminuted,
and moved by currents of water. Amalgamation
presumably originated at that time, although it
was first mentioned in the literature in the 11th
century a.d.
In the Middle Ages, fusion with lead and
cupellation were developed further. Water-
powered crushing machines were also intro-
duced for pulverizing ore, and miners learned to
process arsenic-containing gold ores by roast-
ing.
The alchemists endeavored to manufacture
gold by transmutation of base metals. It was not
until the end of the 18th century that the entire
concept was finally rejected as false. However,
these endeavors led to a better understanding of
chemical processes and to the birth of the true
natural sciences.
The 17th century saw the discovery of sepa-
ration by inquartation, i.e., the separation of gold
and silver by nitric acid, and of affination, i.e.,
separation by sulfuric acid. With advancing in-
dustrialization in the 19th century new methods
replaced the old, but some of the latter have re-
tained some importance to this day. Production
of gold as a byproduct of other metallurgical
processes, (e.g., the refining of copper, zinc, and
lead), played an increasingly important role in
Germany (Rammelsberg/Harz). In 1863, Plat-
tner’s method of chlorination was introduced in
the United States and shortly afterwards in Aus-
tralia. In 1867, Miller succeeded in refining
gold with chlorine. Refining by electrolysis ac-
cording to Wohlwill was introduced in 1878
and is still used for all fine gold of 9995 and 9999
purity. Since 1888, cyanide leaching has permit-
ted economical beneficiation of the Witwater-
srand ores, which were less amenable to other
methods due to the extremely fine distribution
of the gold. Since 1970, conventional cyanide
leaching has been superseded by the carbon-
5
in-pulp process, which dispenses with filtration
of the leached rock powder. More recently, the
ecological problems caused by cyanide leaching
have been overcome by treating the cyanide in
the wastewater with hydrogen peroxide.
The recent expansion of gold production is
also due to the mechanization of ore transporta-
tion and beneficiation. In South America, how-
ever, manual mining of ores is once again being
resorted to. This politically motivated measure,
taken with a view to creating jobs, made em-
ployment possible for 500 000 people.
Solvent extraction is being investigated as a
relatively new method for the rapid and effective
refining of fine gold.
2. Properties [1], [20], [22], [28–37]
The distinction between noble and base metals
is in many ways arbitrary, and is generally deter-
mined by practical considerations and tradition.
Gold is the classic noble metal and complies with
all the criteria for this group of elements: resis-
tance to air, humidity, and to normal wear. Gold
is also remarkable among the metals in that it
occurs in nature almost exclusively in its ele-
mentary state.
2.1. Physical Properties
Gold, atomic number 79, atomic mass
196.96654, has only one naturally occurring
isotope, 197 Au. Its most important radioiso-
tope, which is used in medicine, is 195 Au;
it emits ε and γ rays and has a half-life of
183 d. The electronic configuration of gold
is [Xe] 4 f 14 5 d 10 6 s1 . Its atomic radius is
0.1442 nm. The ionic radius for coordination
number 6 is 0.1379 nm for Au+ , and 0.085 nm
for Au3+ .
Some physical properties of gold are as fol-
lows:
mp 1064.43 ◦ C
bp 2808 ◦ C
Density at 20 ◦ C 19.32 g/cm3
at 900 ◦ C 18.32 g/cm3
at 1000 ◦ C 18.32 g/cm3
at 1065 ◦ C 17.32 g/cm3
at 1200 ◦ C 17.12 g/cm3
at 1300 ◦ C 17.00 g/cm3
6 Gold, Gold Alloys, and Gold Compounds
Vapor pressure at 1064 ◦ C 0.002 Pa
at 1319 ◦ C 0.1 Pa
at 1616 ◦ C 10 Pa
at 1810 ◦ C 100 Pa
at 2360 ◦ C 10 000 Pa
Atomic volume at 20 ◦ C 10.21 cm3 /mol
Electrical resistivity at 0 ◦ C 2.06×10−6 Ω cm
Thermal conductivity at 0 ◦ C 3.14 W cm−1 K−1
Specific heat 0.138 J g−1 K−1
Enthalpy of fusion 12.77 kJ/mol
Enthalpy of vaporization 324.4 kJ/mol
Tensile strength 127.5 N/mm2
The melting point of gold has been a fixed
point on the temperature scale since 1968.
The unit cell of gold is face-centered cu-
bic (type A1), with a lattice constant (a0 ) of
0.40781 nm. Gold as it occurs in nature usu-
ally does not have a very crystalline appearance.
It exhibits threadlike, leaf-shaped, and spherical
forms, on which cubic, octahedral, and dodec-
ahedral surfaces can sometimes be seen. When
large amounts of molten gold solidify, a char-
acteristic pattern of concentric rings appears on
the surface.
Pure gold that has not been mechanically pre-
treated is very soft. Its hardness on the Mohs’
scale is 2.5, and its Brinell hardness is 18 HB.
Gold is the most ductile of all metals. It can be
cold drawn to give wires of less than 10 µm di-
ameter, and beaten into gold foil with a thickness
of 0.2 µm (see Section 8.4). Because of its soft-
ness, gold can be highly polished; this, together
with its noble characteristics and brilliant color,
gives it its yellow luster. The color of utility gold
is less rich and varies considerably according to
its alloy composition (see Chap. 8). Very thin
gold foil is translucent; transmitted light appears
blue-green.
The physical properties of gold and its al-
loys have been thoroughly investigated because
of their significance for modern technology. For
detailed information see [22], [28], [36], [37].
2.2. Chemical Properties [38]
Gold does not react with water, dry or humid
air, oxygen (even at high temperature), ozone,
nitrogen, hydrogen, fluorine, iodine, sulfur, and
hydrogen sulfide under normal conditions.
Sulfuric acid, hydrochloric acid, hydrofluo-
ric acid, phosphoric acid, halide-free nitric acid
(except in very high concentrations), and prac-
tically all organic acids have no effect on gold,
either in concentrated or dilute solutions and at
temperatures up to the boiling point. If a hydro-
halic acid is combined with an oxidizing agent,
such as nitric acid, a halogen, hydrogen perox-
ide, or chromic acid, gold will dissolve. Gold
can also be dissolved in a combination of water
and a halogen (the Plattner process) and in se-
lenic acid. Figure 2 shows the dissolution rates
of gold in the most important industrial agents
used for its dissolution.
Aqueous solutions of alkali metal hydrox-
ides, alkali metal salts of the mineral acids, and
alkali metal sulfides do not attack gold. How-
ever, gold dissolves in solutions of alkali metal
cyanides in the presence of oxygen (see Fig. 2
and Section 4.2) or other oxidizing agents, such
as cyanogen bromide (the Diehl process), 4-
nitrobenzoic acid (see Fig. 2) and 3-nitroben-
zenesulfonic acid, provided they do not rapidly
destroy the cyanide. Gold is also attacked by
sodium thiosulfate solutions in the presence of
oxygen, and by alkali metal polysulfide solu-
tions.
Fused caustic alkalis do not attack gold, pro-
vided air and other oxidizing agents are ex-
cluded. Gold reacts vigorously with alkali metal
peroxides to form aurates. It is inert to the alkali
metal phosphates and borates, and to the alkali
metal salts of the mineral acids, which can there-
fore be used as slagging agents for removing
metallic impurities from gold.
Gold reacts readily with dry chlorine. The
maximum reactivity occurs at 250 ◦ C, and the
minimum at 475 ◦ C. Above 475 ◦ C the reactiv-
ity increases with increasing temperature up to
and beyond the melting point.
Gold can be recovered from solution by elec-
trolytic deposition or by chemical reduction.
If the tetrachloroaurate(III) complex is present,
then iron(II) salts, tin(II) salts, sulfur dioxide,
hydrazine, hydrazonium salts, oxalic acid, or
ascorbic acid can be used as reducing agents.
The very stable dicyanoaurate complex requires
stronger reducing agents such as zinc. Anion ex-
changers, which are used for the recovery of gold
from solutions, sometimes reduce this complex
to metallic gold. Similar results are achieved
with activated carbon.
The standard potential of Au/Au3+ is
+ 1.498 V, of Au/Au+ + 1.68 V, and of
Au+ /Au3+ + 1.29 V.
 Gold, Gold Alloys, and Gold Compounds
Figure 2. Rate of dissolution of fine gold sheet metal in
various oxidizing agents
a) Aqua regia, 6 mol/L; b) HCl, 6 mol/L + Br2 ,
0.2 mol/L; c) NaCN, 0.45 mol/L + 4-nitrobenzoic
acid, 0.1 mol/L + NaOH, 0.2 mol/L; d) HCl, 6 mol/L + Cl2
(saturated); e) HCl, 6 mol/L + H2 O2 , 0.22 mol/L;
f) NaCN, 1 mol/L + air; g) NaCN, 0.45 mol/L + NaOH,
0.2 mol/L + air; h) NaCN, 0.006 mol/L + Ca(OH)2 ,
0.004 mol/L + air
7
Gold can be alloyed with many other met-
als. In classic metallurgical processes (e.g., the
lead blast furnace process and the reverberatory
furnace process for copper ore), gold and silver
follow the same route. Zinc, lead, and copper act
as collecting agents for gold through the forma-
tion of alloys. Gold exhibits the greatest affin-
ity for zinc, followed by lead, and then copper.
Zinc is used to remove gold from molten lead
in the Parkes process (→ Lead). The readiness
with which gold takes up lead, tellurium, sele-
nium, antimony, and bismuth is a disadvantage,
particularly with regard to subsequent mechani-
cal processing. Gold alloys readily with mercury
at room temperature to form an amalgam. The
mercury can be distilled out by heating. This
property is utilized in the amalgamation process
(see Section 4.1), and in fire gilding (see Section
10.8).
Colloidal gold forms hydrosols of an intense
red or violet color, which are relatively resistant
even without protective colloids.
3. Occurrence [1], [2], [6], [20], [40–45]
3.1. Abundance
Gold is distributed very unevenly in the Earth’s
crust, mainly due to enriching processes that
have taken place near the surface. Its average
abundance is very low and is estimated at ca.
0.005 ppm, although widely varying figures are
given.
The gold content of ocean water also varies
greatly, depending on the location. Gold con-
tents of 0.008 – 4 mg/m3 (ppb) have been re-
ported.
3.2. Gold Deposits [7], [11], [44]
The gold deposits which are most easily recog-
nized, and which were the earliest to be disco-
vered, are enriched veins and deposits of gold
particles. These particles were originally present
in primary rock that was worn down by weath-
ering. Enrichment then followed with partial
consolidation due to flowing water. Such de-
posits are known as placer or secondary de-
posits. Typical examples are the relatively small
8 Gold, Gold Alloys, and Gold Compounds
gold deposits in the Rhine Valley, California, and
Alaska. The abundance of gold in placer deposits
fluctuates greatly especially as the gold particles
may be concentrated in very small areas, e.g., a
stream bed. Under favorable conditions, placer
deposits containing as little as 1 ppm gold may
be successfully exploited.
Quartz veins containing gold are often found
along the fault plane of rock fractures. As the
gold particles have remained at their place of
origin, these are termed primary deposits. In
general, it can be assumed that this gold has
been formed hydrothermally, i.e., it has been
through an intermediate stage in aqueous so-
lution. Such deposits are found in East Africa,
Australia, Canada, and the Soviet Union. Their
gold content varies greatly.
The Witwatersrand goldfields in the Repub-
lic of South Africa (Transvaal and Orange Free
State) were also formed by sedimentation. These
are sand and shingle deposits that have been
compacted to form massive rock, in which the
gold is distributed as very fine particles. This
type of gold deposit is known as a conglomer-
ate deposit. The average gold content of the ore
when separated from the gangue is ca. 12 ppm.
Mining reaches a depth of 4000 m where tem-
peratures of 60 – 70 ◦ C can prevail. Work is only
possible here with cooling, which is performed
with chilled air, cooled water, or ice [21]. To
date about one-third of the total world gold pro-
duction has been derived from the Witwater-
srand conglomerate ore. The waste extracted
sand which is found, for example, around Johan-
nesburg, contains about 1500 t gold (0.5 ppm),
mainly contained in pyrites (FeS2 ) which is not
dissolved by cyanide treatment. This material
can also be processed economically.
Sulfidic copper ores may have gold inclusions
which can become highly concentrated as a re-
sult of weathering. In the outer oxidation zone,
hydrothermal reactions take place, such as
while in the underlying cementation zones, the
corresponding back reaction occurs. Such de-
posits are found in Papua New Guinea (Ok Tedi)
and in Brazil. The Ok Tedi deposit contains
about 4 ppm of gold in the cementation zone.
Copper sulfide ores normally contain only a
small proportion of gold (< 1 ppm); however,
they can be a significant gold source. During
smelting, gold accompanies silver and can be
separated in the copper anode slimes. Practically
all silver ores also contain some gold.
3.3. Gold Reserves and Resources
The term reserves denotes those resources
whose existence has been established by
prospecting and for which mining is econom-
ically viable.
World gold ore reserves are assessed at
75 000 t in 1991, or less than 40 times the world
annual primary production [187]. In 1970, gold
reserves were calculated to be one-fifth of this
amount. At that time, the extensive Brazilian
and southeast Asian deposits had not been disco-
vered.
Of the reserves known today, 40 % are found
in the Republic of South Africa, 35 % in Brazil,
and 15 % in Russia/CIS. These are followed
by the United States, Canada, Australia, China,
Borneo, Papua New Guinea, Zimbabwe, and
Ghana, with 1 – 5 % each.
4. Production [1], [2], [20], [27], [35], [39],
[45–56]
4.1. Ore Treatment
In many places, gold is still mined by individu-
als and converted on the spot into marketable
raw gold using simple manual and mechani-
cal processes, such as panning ( gravity sepa-
ration), milling, and amalgamation. Amalgama-
tion is carried out by allowing a slurry of ground
gold-containing ore to flow over mercury-coated
copper plates. The resulting gold amalgam is pe-
riodically removed by scraping. Very fine gold
particles cannot be recovered by these methods,
and in many cases, especially in Brazil, the use
of cyanidation (see Sections 4.2 and 4.3) to ex-
tract the residual gold has been proposed.
Where gold is found in river sands covering
a large area, the ore is often mined and pro-
cessed in floating dredgers. This type of mining
is found, for example, in Siberia, and in the north
of the American continent.
 Gold, Gold Alloys, and Gold Compounds
In the conglomerate gold deposits in Witwa-
tersrand, South Africa, most of the gold occurs
as very fine particles. This means that mechan-
ical enrichment and amalgamation are impossi-
ble, and the gold must be converted to a solu-
ble form by reaction with sodium cyanide. For
this purpose, the gold particles are first released
from the rock material by means of breakers, wet
ball mills, and classifiers. In newer plants, this
milling process takes place underground.
Ground gold ore that contains large gold par-
ticles or sulfides may be unsuitable for cyanida-
tion. Pretreatment, consisting of gravity concen-
tration, generally followed by amalgamation, is
therefore nearly always necessary; this also al-
lows up to 50 % of the gold to be extracted faster
than by the cyanidation process.
Gravity concentration
was formerly carried out using a cord cloth.
The cloth was laid on a suitable support, and a
water slurry of ground ore was passed over it, the
grooves in the cloth being arranged at right an-
gles to the direction of flow. The denser particles
were retained in the grooves, while the lighter
quartz particles flowed away with the water.
The cord cloth has now been replaced by cor-
rugated rubber (thickness 10 mm, groove depth
3 mm, distance between grooves 6 mm). Modern
mechanical equipment has endless belts (width
1.5 m, length 7.2 m), tilted at an angle of 11◦ .
These advance at a speed of 0.4 m/min, against
the direction of flow of the ore slurry. The con-
centrate is sprayed off with water and sent to the
amalgamation plant. In place of endless belts,
slowly rotating cylinders lined with corrugated
rubber are sometimes used (length 3.6 m, diam-
eter 0.9 m, inclination 3.75◦ ).
Concentrates from gravity separation pro-
cesses cannot be directly melted down into gold
bars, because they contain considerable amounts
of iron pyrites and metallic iron. Gold and sil-
ver are therefore generally separated from these
components by amalgamation. The concentrate,
which has a water content of about 70 %, is filled
into a cast iron drum (length 0.9 m, diameter
0.6 m) containing steel balls (diameter 50 mm).
The drum is rotated for 12 h, after which the gold
particles are free from all impurities. Mercury is
then added, and the drum is rotated for a further
2 h. The resulting amalgam is separated from
the other components in a hydrocyclone (diam-
eter 200 mm, inclination 20◦ ); water and excess
9
mercury are removed in a filter press. Remain-
ing mercury is removed by distillation, leaving
an impure mass of spongy gold, which is melted
down into gold bars.
A flotation process is often used before grav-
ity concentration in cases where the gold is
closely associated with pyritiferous materials.
Roasting of ores in air is a secondary process
which is sometimes used after gravity separa-
tion or flotation. The resulting oxides are then
washed and treated by cyanidation. Gold ores
containing sulfidic minerals can also be treated
in a bioleaching process (see → Liquid – Solid
Extraction, Chap. 3.3.3.), which dissolves the
sulfides, exposing the gold particles for subse-
quent cyanidation.
4.2. Cyanidation [48]
The cyanidation process has been used in South
Africa since 1890. In this process, the powdered
mineral slurry, which contains ca. 10 ppm gold
in the solid matter, is treated with an aerated
0.03 % sodium cyanide solution. Black cyanide
(Ca(CN)2 containing carbon and sodium chlo-
ride as impurities), a product of American Cya-
nimid, is often used instead of the more expen-
sive sodium cyanide. The addition of calcium
oxide ensures that the solution remains slightly
alkaline. Dissolution takes place according to
the following reaction:
4 Au + 8 NaCN + 2 H2 O + O2
−→ 4 Na[Au(CN)2 ] + 4 NaOH
The dead powdered mineral is filtered off in
large rotary vacuum filters. The filter cake con-
tains less than a tenth of the original gold content
of the ore. The filtrate is treated with zinc chips,
which are preactivated in lead acetate solution,
to precipitate the gold:
2 Na[Au(CN)2 ] + Zn −→ Na2 [Zn(CN)4 ] + 2 Au
The raw gold is treated with sulfuric acid to
remove excess zinc, dried, and then roasted in
air at 800 ◦ C to oxidize lead, zinc, and iron. A
flux, usually borax, is added, and the material is
melted down to raw gold, with a gold content of
80 – 90 %.
An ecological problem is caused by the pres-
ence of sodium cyanide in the cake of dead rock
10 Gold, Gold Alloys, and Gold Compounds
material and in the wastewater. However, when
exposed to air and sunlight, the cyanide is con-
verted to nontoxic cyanate, and subsequently
carbonate.
4.3. Recovery of Gold with Carbon
[57–69]
The first mention of the ability of carbon to ad-
sorb precious metals was made in 1847. In 1880,
it was found that gold can be recovered from
chlorinated leach liquors by wood charcoal.
McArthur and the Forest brothers discovered
that cyanide was a good lixiviant for gold in 1890
and, in 1894, charcoal was used to recover gold
from cyanide solutions. The charcoal was pre-
pared from wood and did not possess the high
surface area and porosity of carbon today. As
no elution procedure was known, the gold was
recovered from the carbon by smelting. The use
of carbon reached a high point of efficiency in
Australia in 1917 when fine carbon was used
to recover gold from pregnant cyanide solution,
but, as the zinc cementation process advanced,
so interest in the use of carbon dropped off.
In the 1940s, a carbon of higher activity
and greater abrasion resistance was developed
from fruit pips and, in 1952, an elution proce-
dure involving the use of sodium hydroxide and
cyanide (the caustic – cyanide procedure) was
developed. In 1960, a plant using carbon was
erected in Canada, and the first major carbon-in-
pulp (CIP) plant to treat the fraction from which
the coarse material has been removed (slimes)
was built in the United States at Homestake in
1973 to treat 2200 t/d.
Major developments in CIP continued in
South Africa, for treatment of the total cyanided
pulp. By 1976, a small pilot plant was in op-
eration and, by 1978, a plant processing 250 t/d
was on line. The CIP process is now the preferred
method worldwide for the recovery of gold from
cyanided pulp. The only exception appears to be
the Soviet Union, where the resin-in-pulp pro-
cess is used. The CIP process is used for the
treatment of a variety of feed materials rang-
ing from run-of-mine ore to dump materials and
roaster-bed products.
The advantages of the CIP process over zinc
cementation are:
1) Capital costs are lower.
2) Operating costs are lower.
3) The ability of carbon to adsorb gold is not
affected by any of the common constituents
of leach liquors.
4) Carbon is added directly to the cyanided
pulp, and therefore the need for the expensive
filtration and clarification stage is avoided.
5) The losses of soluble gold are usually lower
than in the zinc cementation process.
6) Ores that contain carbonaceous material can
be processed without loss of gold to the car-
bonaceous fraction.
7) Materials that are difficult to filter or thicken
can be treated successfully.
4.3.1. Adsorption of Gold by Carbon
Activated carbon has a porous structure
(→ Carbon, Chap. 5.). The following theories
have been proposed for the mechanism by which
activated carbon loads gold cyanide:
1) complete reduction to metal
2) a chemical precipitation mechanism involv-
ing gold, carbon monoxide, and cyanide
3) physical adsorption of sodium dicyanoau-
rate(I)
4) adsorption of the dicyanoaurate(I) ion
5) ion-exchange adsorption of the dicyanoau-
rate(I) ion
6) adsorption of a neutral complex, whose na-
ture is pH dependent
7) electrostatic interaction between the di-
cyanoaurate(I) ion and positively charged
sites
8) a physisorption process
9) a two-step process, in which an ion pair is
adsorbed onto carbon, and then reduced to
an unidentified species.
The last-mentioned theory is now generally
accepted.
The adsorption of gold cyanide onto activated
carbon is reversible. Thus, an equilibrium exists
between the gold in solution and the gold loaded
on the carbon. Factors which affect the rate of
gold adsorption and those which affect the equi-
librium loading of gold are listed in Table 1.
Certain materials poison activated carbon for
gold adsorption. Calcium carbonate can form in
 Gold, Gold Alloys, and Gold Compounds
the pores and is detrimental to adsorption, but
is removed by acid-washing. Organic materials
(e.g., machine lubricants, detergents, flotation
reagents) also poison carbon to some extent, but
are removed during reactivation. Lower adsorp-
tion efficiencies are attained when a pulp con-
taining calcine, shale, or clay is used, since these
finely divided minerals can block the pores. Cop-
per can decrease efficiency of adsorption by
competing with gold for adsorption sites, par-
ticularly at low concentrations of cyanide.
Table 1. Factors influencing the adsorption of gold by carbon
Factor Effect of increasing the factor
on rate on equilibrium
loading of gold
pH slight decrease decrease
Ionic strength slight decrease increase
Free cyanide slight decrease decrease
Temperature slight increase decrease
Base metals decrease decrease
Carbon particle size decrease none
Mixing intensity increase none
Pulp density decrease none
4.3.2. Carbon-in-Pulp Process
Ores containing 0.25 – 100 g/t gold are pro-
cessed in CIP plants at tonnages from 100 – 106 t
per month. The density of the pulp varies from
1.3 to 1.45 g/cm3 , depending on its viscosity.
A schematic of a CIP plant is shown in
Figure 3. The cyanided pulp is prescreened to
remove coarse material that would otherwise
move with the carbon granules, and might later
block the screens in the CIP circuit. The pulp
then flows through a series of six or eight flat-
bottomed, cylindrical, agitated tanks. The resi-
dence time of the pulp in each stage is ca. 1 h.
Reactivated carbon is added to the last stage,
and is moved countercurrent to the flow of pulp.
The carbon is held in each stage by interstage
screens. The residence time of the carbon in each
stage is 1 – 2 d. The carbon concentration in a
CIP circuit is 15 – 30 g per liter of pulp. The bar-
ren pulp leaving the circuit is screened to remove
fine carbon.
The loaded carbon, which contains
200 – 20 000 g of gold per ton, is removed pe-
riodically from the first stage and eluted with a
caustic – cyanide solution. The carbon is washed
with acid to remove calcium carbonate, and
11
then reactivated at high temperature in a kiln.
The gold in the eluate is generally recovered by
electrowinning.
For reasons of economy, the CIP process is
carried out underground in some mines.
Screening. The total pulp fraction has to
be prescreened at a smaller aperture (0.6 mm,
28 mesh) than that of the interstage screens.
Prescreening removes coarse material to avoid
blocking of the screens further downstream. Two
types of screen are used: (1) vibrating screens
with woven wire or polyurethane mesh, and (2)
linear moving-belt screens.
Wood chips constitute a small fraction of
the incoming pulp, and cause problems further
downstream when vibrating screens are used.
Another prescreening device, such as a dummy
tank, is then required. A dummy-tank is a closed
circuit tank in which the pulp passes through
submerged air-cleaned screens to remove wood
chips.
Interstage screens are used to retain car-
bon while allowing the finer pulp to flow down
through the train.
The two types of screen that are used are ex-
ternal and submerged. With external screens, the
pulp is air lifted onto the screens (normally vi-
brating decks), and transferred to the next stage,
while the carbon is returned to the stage from
which it came. A number of submerged screens
have been developed. Air-cleaned screens nor-
mally use square metal mesh, while mechani-
cally cleaned screens use wedge-wire. Duties on
these screens vary from 50 to 200 m3 of pulp per
square meter of screen per hour. The aperture of
the screens is 0.8 mm (20 mesh). The size of the
carbon particles used in CIP is 1 – 2 mm (8 to 16
mesh), although larger particles are used when
problems are encountered with screening.
Abraded carbon resulting from breakage of
the carbon in the CIP circuit is recovered from
the barren pulp by a final screen. The units and
apertures of this screen are similar to those used
for prescreening.
Interstage movement of carbon is
achieved using airlift pumps, vertical spindle
pumps, centrifugal pumps, or peristaltic pumps.
Factors that affect the choice of pump are con-
trollability, carbon wear, and operating costs. In
most plants, carbon is transferred intermittently,
12 Gold, Gold Alloys, and Gold Compounds
Figure 3. Schematic of the carbon-in-pulp circuit
a) Prescreening; b) Final screening; c) Regeneration; d) Elution; e) Electrowinning
but may also be transferred continuously. The
following methods are used:
1) Loaded carbon is removed from stage one,
the carbon in stage two is then transferred to
stage one, and so on down the train.
2) Regenerated carbon is added to the last stage,
the carbon in the last stage is then transferred
to the second-last stage, and so on up the
train.
3) All the pumps are turned on to transfer the
carbon in each stage to the next stage up the
train.
Agitation. The optimum agitation system
provides a high pulp flow and low shear to avoid
carbon breakage. Mechanical agitation is fa-
vored over air agitation because it consumes less
power, provides better “live” vessel volume, and
has acceptable carbon-attrition rates. Draft tubes
and open-impeller agitators are used. Power in-
puts vary from 0.015 to 0.2 kW/m3 of pulp.
Elution. The gold capacity of carbon de-
creases with increasing temperature. Increasing
the concentration of cyanide and hydroxide ions
also decreases the capacity of the carbon for
gold.
These two facts were exploited by Zadra in
1952 to develop the first efficient elution tech-
nique to remove gold from carbon. Other elution
procedures have since been developed.
The Zadra process involves the recycling of
a solution containing 1 – 2 % sodium cyanide
and 1 – 2 % sodium hydroxide through a bed of
carbon. The temperature is over 85 ◦ C, and the
flowrate is about one bed volume per hour. The
elution takes 48 h to complete. An electrowin-
ning cell is used to recover the gold from the
eluate. The advantages of this system are that
the capital costs are low, the process is simple,
and the reagent consumption is low. Its major
disadvantage is that the rate of stripping is slow.
The AARL process, which was developed by
the Anglo American Research Laboratories, has
two stages. In the first stage, the carbon is pre-
soaked under pressure at a temperature above
115 ◦ C, in a solution containing 1 – 5 % sodium
cyanide and 1 – 5 % sodium hydroxide for sev-
eral hours. In the second stage, the carbon is
eluted with five to seven bed volumes of water
at 50 – 100 kPa and above 110 ◦ C for 5 h at a
flowrate of three bed volumes per hour. The ad-
vantages of this procedure are that elution is fast
and the gold concentration in the eluate is high,
which leads to efficient electrolysis. Its disad-
 Gold, Gold Alloys, and Gold Compounds
vantages include the need for high-quality water,
more expensive equipment than that used by the
Zadra process, and higher reagent consumption.
Elution with Organic Solvents. The addition
of, for example, a 20 % solution of ethanol to
a caustic – cyanide eluant increases the rate of
elution, which takes ca. 6 h at atmospheric pres-
sure and 80 ◦ C. Disadvantages include higher
reagent costs and handling problems associated
with organic solvents.
The high-pressure stripping process is sim-
ilar to the Zadra process, except that elution is
carried out at up to 160 ◦ C and at ca. 350 kPa. It
has the advantages of lower reagent consump-
tion, smaller elution inventory, and a smaller
elution circuit. Disadvantages are more costly
equipment, and that effluent solutions have to
be cooled to avoid flashing.
Gold Recovery. The gold is recovered from
the eluate either by zinc precipitation or by elec-
trowinning. A number of electrowinning cells
have been developed.
The Zadra cylindrical cell consists of a cylin-
drical core (polypropylene basket), which con-
tains steel wool and acts as the cathode. The
anode (stainless steel) surrounds the cathode in
the cell, and the eluate is pumped into the center.
The most commonly used cell is the Mintek
cell. It has a rectangular configuration with alter-
nating anodes and cathodes in parallel, similar to
those in copper-electrowinning cells. The cath-
odes are removable plastic baskets with perfo-
rated sides, packed with steel wool. The anodes
are perforated stainless-steel plates. The flow of
eluate is parallel to the flow of current.
Regeneration of carbon is carried out in
two stages: (1) washing with acid to remove cal-
cium carbonate and some base metals, and (2)
thermal reactivation to remove organic materials
and reexpose the pore structure.
The loaded carbon is washed with a 5 % so-
lution of hydrochloric acid for 6 h at 75 ◦ C in a
column constructed of Hastelloy or rubber-lined
mild steel. The carbon is then neutralized with
sodium hydroxide. Acid-washing can be carried
out before or after elution, but is generally done
first because this increases the efficiency of elu-
tion.
In thermal reactivation, the degree of activa-
tion increases with increasing temperature and
13
residence time, but micropores are destroyed if
the conditions are too harsh. Reactivation is typi-
cally carried out at 700 ◦ C for 10 min. Air should
be excluded during regeneration. The steam gen-
erated from the carbon is normally sufficient to
exclude air. The regenerated carbon is normally
cooled by quenching in water.
Regeneration is usually carried out in a ro-
tary kiln, which is heated externally by electrical
resistive windings. In the Rintoul furnace, heat-
ing is achieved by passing an electric current
through a bed of predried carbon in the presence
of steam.
4.3.3. Carbon-in-Leach Process
Some ores contain carbonaceous material that
is slightly active and can adsorb dissolved gold.
These carbonaceous materials are termed preg-
robbers. When a preg-robber is present in an
ore, the carbon-in-leach (CIL) process is used, in
which cyanidation and carbon adsorption occur
in the same reactor.
The CIL circuit is similar to a CIP circuit, the
main difference being the residence time of the
pulp, since in CIL this is determined by the rate
of gold dissolution and not by the rate of gold
adsorption as in CIP. Hence, residence times of
4 h per stage are used. The presence of activated
carbon prevents the preg-robber from adsorbing
gold.
5. Gold Refining [1], [20], [27], [35], [39],
[46], [47], [51], [53], [55]
5.1. Chemical Refining [2], [70]
The historical methods for separating gold from
silver depended on dissolving silver and any ac-
companying base metals from solid solutions
containing gold, using either nitric acid (inquar-
tation) or sulfuric acid (affination) (Section 1.3).
They were accepted up to the second half of the
nineteenth century as the best way of manufac-
turing relatively pure gold. However, the exclu-
sive use of these methods is insufficient today,
and they must hence be combined with the other
purification steps described below.
14 Gold, Gold Alloys, and Gold Compounds
A method which allows recovery of relatively
pure gold is to dissolve the raw gold in hy-
drochloric acid in the presence of an oxidizing
agent. Silver chloride precipitates and can be re-
moved, while gold is precipitated by reduction
with oxalic acid or other reducing agents like
FeCl2 , FeSO4 , SO2 , or Na2 SO3 . However, a sin-
gle reductive precipitation process is usually in-
sufficient, as part of any palladium present is
entrained by the gold. If sulfur dioxide is used
instead, the same applies to copper, nickel, zinc,
and lead. Precipitation and separation normally
have to be repeated several times before fine gold
of sufficient purity is obtained. This method has
therefore only found acceptance in cases where
the commoner processes (see Sections 5.2 and
5.3) have not been established, either because
the amounts involved are too small, or because
the need arises only sporadically or in combi-
nation with other raffination processes like elec-
trolysis. However, acid dissolution has several
advantages: the metal is tied up for a short time
only; a high yield of gold can be obtained in a
single process step; and conventional equipment
can be used.
5.2. Miller Process [71]
The Miller process has been of commercial sig-
nificance since the 1870s. Probably more than
two thirds of all gold produced to date has been
through this process. It is extremely economi-
cal, and the gold quality obtained (99.5 – 99.6 %)
meets the requirements of the gold trade. The
largest plant in the world is the Rand Refinery
in Gerniston, Republic of South Africa, which
refines all the gold from South African mines,
as well as that from neighboring countries. The
Miller process is used not only by the mining
companies of almost all gold-producing coun-
tries, but also in recycling processes.
The Miller process is based on the fact that
gold chlorides are unstable above 400 ◦ C, and
thus do not form at a reaction temperature of
ca. 1100 ◦ C, whereas silver and base metals re-
act with chlorine to form stable chlorides. At
this temperature, AgCl (bp 1554 ◦ C) and CuCl
(bp 1490 ◦ C) are molten and therefore collect
in a slag layer, which is considerably less dense
than molten gold. The chlorides of the other met-
als volatilize at the reaction temperature, for ex-
ample, PbCl2 (bp 954 ◦ C), FeCl2 (bp 1023 ◦ C),
FeCl3 (bp 319 ◦ C), ZnCl2 (bp 732 ◦ C), and
CuCl2 (bp 655 ◦ C). As the process is effective
when only a slight excess of chlorine is used,
the amount of CuCl and FeCl2 formed is greater
than that of CuCl2 and FeCl3 .
The raw gold delivered to the Rand refinery
is weighed to an accuracy of 0.01 oz and then
melted in an induction furnace. Four samples are
taken and analyzed for gold content. The gold is
cast into bars and reweighed. The gold content
of the whole load is then determined. The bars
are remelted in an induction furnace in batches
of 500 kg, and chlorine gas is passed into the
molten metal through quartz pipes, at a pressure
of 0.2 kPa. First, the chlorine reacts selectively
with iron, zinc, and lead (Fig. 4), whose chlo-
rides are volatile at the reaction temperature and
are thus removed as vapors. Finally, silver and
copper chlorides form (Fig. 4). These are molten
at the reaction temperature and thus form a slag
which floats on the molten gold. Borax is added
to the slag as a flux. The end point of the reaction
is indicated by the appearance of red gold chlo-
ride vapor, and is confirmed by taking a sample
for analysis. The silver content, which is deter-
mined by X-ray fluorescence analysis, must be
below 0.4 %. After pouring off the slag, the gold
is poured into tared molds.
Figure 4. Decrease in the concentration of impurities in
gold as a function of chlorination time
∗ Expressed as a percentage of the initial metal content. Typ-
ical starting concentrations, wt %: Ag 9.0, Cu 1.4, Pb 0.35,
Fe 0.18, Zn 0.06
The chloride slag is ground and screened.
Entrained gold is separated and returned to the
process. Copper(I) chloride is oxidized to cop-
per(II) chloride using sodium chlorate solution
containing hydrochloric acid, and dissolved. The
 Gold, Gold Alloys, and Gold Compounds
solution is filtered and copper is cemented. Sil-
ver chloride is reduced with zinc in aqueous so-
lution, and sent to a silver-refining electrolysis
process.
Platinum-group metals cannot be separated
by the Miller process (Fig. 5), as their chlorides,
like those of gold, do not exist at the reaction
temperature. However, this is not a disadvan-
tage for gold from the Witwatersrand deposits,
as this is free from platinum-group metals.
Figure 5. Thermodynamic of the Miller process [22, p. 39]
(Courtesy Giesel Verlag).
1) Pt + 2 Cl2 −→ PtCl4 ;
2) Pt + 2 Cl2 −→ PtCl2 ;
3) Au + 1 12 Cl2 −→ AuCl3 ;
4) Au + 12 Cl2 −→ AuCl;
5) Ag + 12 Cl2 −→ AgCl;
6) Cu + 12 Cl2 −→ CuCl;
7) Cu + Cl2 −→ CuCl2 ;
8) Ni + Cl2 −→ NiCl2 ;
9) Fe + Cl2 −→ FeCl2 ;
10) Pb + Cl2 −→ PbCl2 ;
11) Zn + Cl2 −→ ZnCl2 ;
12) Fe + 1 12 Cl2 −→ FeCl3
The great economic advantage of the Miller
process, in addition to low production costs, lies
in the fact that the gold leaves the refinery in
a marketable form, thus minimizing the finan-
15
cial losses due to tying up of the metal. To meet
requirements for higher purities, Wohlwill Elec-
trolysis may follow in addition.
5.3. Wohlwill Electrolysis [27], [72], [73]
The Wohlwill electrolytic refining process for
gold was developed in 1878 at the Norddeutsche
Affinerie in Hamburg. It is still indispensable for
the industrial production of fine gold of qual-
ity ≥ 99.9 % (in practice usually 99.95 % and
99.99 %).
The Wohlwill process uses an electrolyte
containing 2.5 mol/L of hydrochloric acid and
2 mol/L of tetrachloroauric acid. Electrolysis is
carried out with agitation at 65 – 75 ◦ C. The raw
gold is introduced as cast anode plates. The cath-
odes, on which the pure gold is deposited, were
for many years made of fine gold of thickness
0.25 mm. These have now largely been replaced
by sheet titanium or tantalum cathodes, from
which the thick layer of fine gold can be peeled
off. In a typical electrolysis cell (Fig. 6), gold
anodes weighing 12 kg and having dimensions
280 × 230 × 12 mm are used. Opposite them are
conductively connected cathode plates, arranged
two or three on a support rail. One cell nor-
mally contains five or six cathode units and four
or five anodes. The maximum cell voltage is
1.5 V and the maximum anodic current density
1500 A/m2 . At the anode, the reaction
Figure 6. Wohlwill electrolysis cell
Au + 4 Cl− −→ [AuCl4 ]− + 3 e−
takes place, and at the cathode the reverse re-
action. Some of the gold dissolves anodically as
gold(I)
Au + 2 Cl− −→ [AuCl2 ]− + e−
16 Gold, Gold Alloys, and Gold Compounds
Anodes and cathodes are normally replaced ev-
ery two days. About 10 % of the anode gold,
especially parts located above the electrolyte, is
remelted to form new anodes. The anode slime
is collected in a trough in the bath. In addi-
tion to silver chloride, it contains rhodium, irid-
ium, ruthenium, and osmium, which can be reco-
vered, and approximately 10 % of the anode gold
formed by the reaction
3 AuCl + HCl −→ 2 Au + H[AuCl4 ]
Platinum and palladium can be recovered from
the electrolyte, which also contains copper, iron,
and nickel.
The accumulation of metallic impurities in
the electrolyte, and of anode slime in the cell,
means that the electrolyte can only be used for a
limited period of time. Therefore, the material to
be refined should have a high gold content (gen-
erally > 95 %) and it is often best to use gold
which has already been through the Miller pro-
cess. Especially the silver content should not be
too high to avoid passivation of the anodes by
formation of insoluble chloride films. The gold
quality of the cathode deposits depends on the
condition of the electrolyte, and on the amount
of anode slime that has collected in the cell. A
purity of 99.9 % is considered to be a minimum,
which is the quality of Russian commercial gold.
Today, 99.99 % can be considered as the norm,
rather than 99.95 %. Sometimes anode bags are
used to increase the purity of the gold.
The great advantage of the Wohlwill electrol-
ysis process is the high purity of the gold pro-
duced. In addition, the byproducts, especially
platinum-group metals, are also relatively easy
to isolate. A disadvantage is the fairly long pe-
riod during which the noble metal is tied up,
leading to considerable financial losses.
World capacities for Wohlwill electrolysis are
very large. In the Republic of South Africa, ap-
proximately a quarter of all gold from primary
production, after it has gone through the Miller
process, undergoes final purification to fine gold
by Wohlwill electrolysis. In the Soviet Union,
all gold is treated by electrolysis, as it normally
contains platinum-group metals. Practically all
noble-metal parting works which recover gold
from secondary materials are dependent on elec-
trolytic refining, again because platinum-group
metals are normally present. Today, almost ex-
clusively fine gold (99.99 %) is used, both for
industrial purposes, and for investment; trad-
ing countries such as Switzerland therefore have
large refining capacities, mainly producing gold
of a quality between “good delivery” (99.5 %)
and 99.99 %.
Chemical reactions (see Section 5.1) for the
refining of gold have both advantages and disad-
vantages in comparison to electrochemical reac-
tions. While Wohlwill electrolysis has low op-
erating costs, it needs a high hold up of gold
as electrolyte and residual anode. The chemical
reactions can be used for different kinds of gold-
containing input material and are carried out in
multipurpose vessels. However, the demand for
chemicals and the amount of off-gas produced
are higher.
5.4. Solvent Extraction [74], [75]
Tetrachloroauric(III) acid can be extracted from
aqueous solution by many organic solvents. Sol-
vents which can form metal complexes (e.g.,
ethers and esters) are most effective. Total sep-
aration from the usual accompanying elements
cannot, however, be achieved.
With the exception of dibutyl carbitol, no sys-
tems have yet been discovered which can be ap-
plied commercially. Yet a system with a high
degree of separation efficiency and simple pro-
cess management, including stripping the pure
gold, could offer considerable advantages over
currently used methods, even concerning the ab-
sence of a gold stock.
6. Recovery of Gold from Secondary
Materials [1], [3], [20], [27], [35], [46],
[47], [76–81]
6.1. Recovery from Gold Alloys
For the recovery of gold from alloys with a gold
content of more than 30 %, the Miller process
(see Section 5.2) is the most economical method.
This also applies to the treatment of anode slimes
from the electrolytic refining of silver (→ Silver,
Silver Compounds and Silver Alloys), providing
these have a high gold content and can be melted.
For small quantities of gold-rich alloys, a use-
ful treatment is dissolution in hot aqua regia, or
 Gold, Gold Alloys, and Gold Compounds
in hydrochloric acid (usually at 20 – 50 ◦ C) con-
taining a halogen or hydrogen peroxide. Silver
precipitates as sparingly soluble silver chloride.
Relatively pure gold is recovered from the so-
lution by selective reduction. If copper and lead
ions are present, the best reducing agents are
sulfur dioxide or hydrazine; if platinum-group
metals are present, oxalic acid is used.
In the case of gold – copper alloys, which also
may contain silver and nickel, treatment with
aerated dilute sulfuric acid allows the separa-
tion of noble metals from base metals. Gold can
only be separated from base metals in this way
if the gold content of the alloy is less than ca.
65 %, and the material has been finely milled or
powdered.
There are two historically important
processes for treating gold – silver or
gold – silver – copper alloys. The silver may
be dissolved with nitric acid, preferably after
realloying to a silver to gold ratio or a silver
and copper to gold ratio of 3 : 1 (inquartation);
or hot concentrated sulfuric acid can be used
(affination). The latter process is rarely used
today. Silver – copper alloys with a low gold
content are not suited to the above process, but
can be treated in noble-metal works by the lead
cupellation process (see Section 6.2). Lead is
removed as litharge, PbO, which also takes up
copper as CuO, and other metal and metalloid
oxides, leaving behind doré silver. This is sub-
jected to electrolytic refining (→ Silver, Silver
Compounds and Silver Alloys); gold collects in
the anode slime.
6.2. Recovery from Sweeps
The noble-metal processing industry produces
large amounts of waste dust and debris, known
as sweeps (e.g., slag, ash, soot, precipitation
and emulsion residues, and sweepings). The
gold content of these materials is mostly in the
range 0.5 – 10 %. Usually they are first care-
fully ground, screened, and, if necessary, dried
or burned. The fine nonmetallic fraction and the
coarse metallic fraction, which can usually be
melted, are analyzed separately.
The usual method for treating gold-con-
taining sweeps is to melt the material down, to-
gether with silver-containing sweeps, in a lead
shaft furnace. Depending on the composition of
17
the sweeps, calcium carbonate, silicic acid, lead
oxide, carbon, and materials containing sulfur
are added. The mixture of powdered compo-
nents is normally briquetted, pelletized, or sin-
tered before being fed into the shaft furnace. The
metallic phase (alloy) produced in the furnace
contains lead and almost all of the noble metal.
This alloy is then converted to doré silver (a few
percent Au; < 0.1 % Pb; the balance is Ag) in
a cupel furnace (→ Silver, Silver Compounds
and Silver Alloys) by oxidizing lead to lead(II)
oxide. The silicate slag from the shaft furnace
contains a negligible quantity of noble metal,
and can usually be discarded. The slagging pro-
cess may have to be repeated, for example if
the noble-metal content exceeds 300 ppm. In the
sulfidic phase, which forms between the metallic
phase and the slag, almost all the copper collects
with the nickel to form copper matte. The rela-
tively high content of silver and valuable non-
ferrous heavy metals in the copper matte makes
special treatment necessary; this is usually car-
ried out at copper smelting works.
When raw gold is refined (see Chap. 5), the
resulting residues contain more gold than silver.
These substances are treated in a shaft furnace
and then in a refining furnace, together with raw
silver from the Miller process. Unlike other py-
rometallurgical recycling methods for silver and
gold, a copper matte phase is not formed in the
shaft furnace. The Au : Ag ratio is normally 1 : 4.
6.3. Recovery from Surface-Coated
Materials
Surface coatings containing gold come mainly
from the electronics industry, plus a small pro-
portion from the jewelry industry and electri-
cal engineering. The base material is essentially
metallic; the gold coatings are often only a few
micrometers thick, but may account for a gold
content between a few tenths percent and a few
percent.
The most economic solution is usually to re-
move only the gold coating, and to send the un-
derlying base material directly to a recycling
process. Mechanical pretreatment is often re-
quired to expose the gold surface. Depending
on the particular combination of materials and
the degree and type of finishing employed, this
can be carried out with a shredder, jaw crusher,
18 Gold, Gold Alloys, and Gold Compounds
or edge runner. Frequently, this is followed by
air separation, gravity separation, or magnetic
separation to remove the ballast materials. It is
normally not advisable to burn off plastic mate-
rials because the gold diffuses into the metallic
base, and it is then impossible to remove it all.
For this reason it is preferable to decompose the
plastic material by pyrolysis.
To remove the gold from the metallic base,
the material is usually agitated in alkaline
cyanide solutions (10 – 20 g/L NaCN). Air is
only rarely used as an oxidizing agent, because
of the relatively low rate of dissolution. In-
stead, water-soluble aromatic nitro compounds
(e.g., nitrobenzoic acid or nitrobenzenesulfonic
acid) are normally employed. Potassium peroxo-
disulfate and hydrogen peroxide are also suit-
able, but they have a greater tendency to oxidize
the cyanide ion. The base materials (e.g., iron,
nickel, and cobalt) are attacked only to a lim-
ited extent during the dissolution process. When
the base material is composed of copper, or a
copper-rich alloy, zinc cyanide or lead salts are
usually added as inhibitors to keep them from
being attacked.
The gold is recovered from cyanide solution
by adding zinc powder (see Section 4.3), after
any excess oxidizing agent has been reduced
with hydrazine or formaldehyde. The gold can
also be recovered by electrolysis, using insol-
uble graphite or magnetite anodes (100 A/m2
cathode, 3 – 4 V), or platinized titanium anodes.
Excess oxidizing agent should also be reduced
to obtain optimum current efficiency and speed
of deposition. In addition to the reductive de-
position of gold, thermal decomposition of the
dicyanoaurate(I) complex is also possible.
Gold-plated metallic wastes can also be di-
rectly deplated by electrolysis, preferably in
electroplating drums used as anodes. The gold is
recovered in metallic form from the cathode in
a single step. The method is, however, not very
well suited to the recovery of gold from bulk
material in anode baskets, because the electric
field is screened off from the material at the cen-
ter of the load, and as a result not all the gold is
removed.
Gold can be extracted from solutions with
a very low gold content (≤ 0.1 g/L) by anion-
exchange resins (e.g., Lewatit M 500) [80] or ac-
tivated charcoal [81]. However, elution is costly
and usually incomplete; the gold-loaded carriers
are therefore most frequently ashed, and the gold
recovered from the ash. The solutions are not
returned to the deplating process because they
contain degradation products, especially from
organic nitro compounds, which would interfere
with the process.
The methods described above can also be
used to treat other cyanide gold solutions, e.g.,
unusable electroplating baths.
Gold-plated materials are occasionally
smelted together with copper ores in large
copper-smelting works. In addition to silver,
these ores always contain some gold. A dis-
advantage of this method is the long time the
gold has to stay in the process. Gold collects
in the anode slimes during electrolytic refining
of the copper and can be recovered from these.
All gold concentrates recovered using the pro-
cesses described here still require refining (see
Chap. 5).
7. Gold Compounds [1], [12], [20], [38],
[45], [70], [82–86]
Almost all gold compounds occur in the oxi-
dation states + 1 and + 3. The oxidation states
+ 2 and + 5 are also known. Bimetallic com-
pounds of gold(II) are usually mixed valence
compounds containing gold(I) and gold(III).
The generally very low stability of binary
gold(I) and gold(III) compounds based on ionic
bonding can be ascribed to the structure of the
two outer electron shells. The ten electrons of
the 5d level and the single electron of the 6s
level differ only slightly in energy. Therefore,
ionization of the 6s1 electron to leave a 5s2 p6 d 10
valence shell, i.e., the reaction Au → Au+ , is en-
ergetically not particularly favorable. Gold(III)
compounds with the 5s2 p6 d 8 valence shell ex-
hibit a tendency to fill the 5d level. Thus, the
electron-acceptor effect is strong, and the com-
pounds are strong oxidizing agents. The simulta-
neous participation of both outer electron shells
gives rise to properties characteristic of the tran-
sition metals, such as variable oxidation state,
colored compounds, and the tendency to form
complexes.
7.1. Potassium Dicyanoaurate(I)
Properties. Potassium dicyanoaurate(I)
[13967-50-5], K[Au(CN)2 ], M r 288.10, d
 Gold, Gold Alloys, and Gold Compounds
3.452 g/cm3 , forms colorless crystals which
are readily soluble in water and alcohol, but
insoluble in acetone and ether. The solubility
in water is strongly dependent on the temper-
ature (Fig. 7). The effect of potassium cyanide
concentration on the solubility of potassium di-
cyanoaurate is shown in Figure 8. The complex
is neither air nor light sensitive and is stable in
aqueous solution above pH 3.
Figure 7. Solubility of potassium dicyanoaurate(I) in water
as a function of temperature
Preparation [70], [87]. Potassium di-
cyanoaurate is prepared from fulminating gold,
from gold(III) hydroxide, and by electrolysis.
The third method is now the most common
preparation from fulminating gold is potentially
hazardous.
From Fulminating Gold. Fulminating gold is
precipitated from a solution of tetrachloroau-
ric(III) acid by addition of excess aqueous am-
19
monia; the precise composition of the precipi-
tate is not known. The chloride content of the
precipitate decreases with increasing excess of
ammonia.
Fulminating gold must not be allowed to dry,
since it is highly explosive in this state. The ful-
minating gold must be thoroughly washed with
deionized water to remove chloride, since chlo-
ride ions interfere in electroplating processes.
After washing, the precipitate is dissolved in
a small excess of potassium cyanide solution.
This is followed by filtration, concentration, and
crystallization. The mother liquor is repeatedly
reused in the process.
Electrolysis. When a gold anode is dissolved
in aqueous potassium cyanide, potassium di-
cyanoaurate(I) is formed with hydrogen being
liberated at the cathode. To prevent the di-
cyanoaurate(I) ion from being electrolyzed at the
cathode with deposition of gold, a diaphragm is
used. Fluoropolymer-based ion-exchange mem-
branes are used for this purpose. The mother
liquor is reused or worked up following crystal-
lization of the potassium dicyanoaurate(I). This
can be carried out under particularly mild con-
ditions by using the continuously-cooled crys-
tallization process. Cyanide and chloride are the
major impurities. Electrolysis produces potas-
sium dicyanoaurate(I) with a particularly low
chloride content, which depends solely on the
quality of the potassium cyanide and of the wa-
ter.
From Gold(III) Hydroxide. Instead of fulmi-
nating gold, gold(III) hydroxide may be reacted
with potassium cyanide solution. Precipitation
of gold(III) hydroxide from tetrachloroauric(III)
acid by addition of an alkali metal hydroxide
does not always go to completion. Aging of the
gold(III) hydroxide considerably reduces its rate
of dissolution in potassium cyanide solution.
Uses and Economic Aspects. Potassium di-
cyanoaurate(I) serves as the gold component
in the baths commonly used for electroplating
and to a lesser extent in electroless plating
(→ Electrochemical and Chemical Deposition,
Chap. 8.9.). Plating baths with higher acidity are
based on tetracyanoaurate (III) [88].
With increasing utilization of gold-plated
electronic components, the demand for gold
plating baths, and hence for potassium di-
cyanoaurate(I), has grown considerably. In 1997
20 Gold, Gold Alloys, and Gold Compounds
ca. 6 % of the 3890 t of gold processed annually
in the world was used by the electronics indus-
try. In the jewelry industry, too, that demand has
increased as a result of rolled gold being super-
seded by electroplating with hard gold.
Figure 8. Dependence of the solubility of potassium di-
cyanoaurate(I) in water upon the concentration of potassium
cyanide at 20 ◦ C and at 0 ◦ C
7.2. Tetrachloroauric(III) Acid
Properties. Tetrachloroauric(III) acid
[16903-35-8], H[AuCl4 ], M r 411.85, crystal-
lizes as a tetrahydrate in the form of light yel-
low, deliquescent crystals. It is readily soluble
in water, soluble in alcohol and ether, and is
corrosive.
Preparation [70]. Tetrachloroauric acid is
prepared by dissolving gold in warm aqua re-
gia. In order to remove residual nitric acid, the
solution is concentrated by evaporation with re-
peated addition of hydrochloric acid, and the
resulting melt is poured into porcelain dishes.
Moisture must be excluded while the melt cools,
solidifies, and is finally powdered. Crystalliza-
tion from the aqueous mother liquor produces
an extremely hygroscopic material. Instead of
nitric acid, other oxidants (e.g., chlorine) may
be added to the hydrochloric acid. The high rate
of dissolution of aqua regia is only rarely at-
tained (see Fig. 2), but the pollution caused by it
is lower and control of the reaction is simpler, es-
pecially under industrial conditions. Care must
be taken to assure removal of any excess oxi-
dants and their reaction products. Tetrachloroau-
ric(III) acid can also be prepared by anodic dis-
solution of gold in hydrochloric acid, but this
requires the use of a diaphragm.
Uses [1]. Tetrachloroauric(III) acid is used to
prepare other gold compounds. It is also used to
make gold ruby glass, gold purple (Purple of
Cassius), and purple colorants for enameling of
ceramics (→ Ceramic Colorants) and to prepare
the electrolyte for the Wohlwill electrolysis.
7.3. Sodium Disulfitoaurate(I)
Properties. Sodium disulfitoaurate(I)
[39394-92-8], Na3 Au(SO3 )2 M r 426.06, is rela-
tively unstable in the solid state, and is therefore
not isolated as crystals for industrial use. It is
stable in weakly alkaline solutions above pH
8.5, even upon heating and when exposed to
light.
Preparation. Sodium disulfitoaurate(I) is
prepared from fulminating gold or from gold(III)
hydroxide.
 Gold, Gold Alloys, and Gold Compounds
From Fulminating Gold. Fulminating gold
(see Section 7.1) is dissolved with stirring in a
dilute solution of sodium hydrogen carbonate;
sodium sulfite is then added. The reaction mix-
ture is stirred at 70 ◦ C until it clears. The pH
must be maintained above 9. This is achieved
by addition of sodium hydrogen carbonate solu-
tion. In order to remove ammonia, the solution
is heated to about 90 ◦ C with the simultaneous
introduction of air. The gold content of the so-
lution is kept at ca. 100 g/L by evaporation or
by dilution with deionized water. This concen-
tration is desirable for electroplating purposes.
Instead of sodium sulfite, gaseous sulfur diox-
ide and a correspondingly higher quantity of
sodium hydroxide solution may be used; the pH
is controlled as described above.
From Gold(III) Hydroxide. Instead of fulmi-
nating gold, gold(III) hydroxide may be used.
The reaction takes place under approximately
the same conditions as with fulminating gold.
The disadvantages are the same as in the
preparation of potassium dicyanoaurate(I) from
gold(III) hydroxide (see Section 7.1).
Uses. Sodium disulfitoaurate(I) is sometimes
used in preference to potassium dicyanoaurate(I)
in electroplating baths. These baths are espe-
cially advantageous for the production of duc-
tile and wear-resistant coatings and in white-
gold and rose-gold electroplating. Their disad-
vantages are difficult handling, shorter service
life, and higher price. Their low toxicity is coun-
terbalanced by problems in waste water disposal,
e.g., those caused by the ethylenediaminetetra-
acetic acid (EDTA) complexes of the alloying
elements.
Sodium disulfitoaurate(I) is increasingly be-
ing replaced by the corresponding ammonium
salt, which provides special advantages with
Au – Pd – Cu baths, such as the facility to pro-
duce very dense coatings.
7.4. Miscellaneous Gold Compounds [1],
[20], [70], [89]
Bright gold preparations (gold sulforesinates)
are used for gilding ceramics and glass
(→ Ceramic Colorants). Other compounds,
some of which have applications in prepara-
tive and analytical chemistry, include gold(III)
21
chloride AuCl3 , gold(I) chloride AuCl, gold(III)
hydroxide Au(OH)3 or AuO(OH), gold(III)
oxide Au2 O3 , the gold sulfides Au2 S, AuS, and
Au2 S3 , gold(I) cyanide AuCN (→ Cyano com-
pounds, Inorganic, Chap. 2.3.4.), and gold(I)
acetylide Au2 C2 . Sodium dithiosulfatoaurate(I),
Na3 [Au(S2 O3 )2 ] · 2 H2 O, is used as a pho-
tographic sensitizer, and gold(III) selenate,
Au2 (SeO4 ), for staining glass.
([90], [91]): Gold compounds, partic-
ularly gold thiosulfate, gold mercaptides,
and gold malate, have long been used
for the treatment of rheumatic disease
(→ Anti-inflammatory – Antirheumatic Drugs,
Chap. 4.1.). The triethylphosphine gold com-
plex of thioglucose tetraacetate, Auranofin
[34031-32-8], is very effective against chronic
inflammation of joints. Gold(I) complexes of
diphosphines may be beneficial in tumor ther-
apy. Gold(I) and gold(II) complexes have an-
timicrobial activity.
8. Gold Alloys [1], [12], [20], [28], [35],
[45], [92–103]
Because of its mechanical softness, gold is, like
most other noble metals, used in elemental, un-
alloyed form only in special functions in elec-
tronics, sensors, optical devices, and catalysts.
For the majority of applications, gold must be
alloyed to adjust its mechanical (strengthening),
thermal, physical (electrical, color), and struc-
tural (grain refining) properties according to spe-
cial requirements.
The practical uses of gold alloys and of fine
gold are mainly determined by their color, hard-
ness, corrosion resistance, melting point, and
relative value. The degree of hardness can be
controlled by heat treatment. The melting point
plays a significant role during manufacture and
processing.
Structure Types. Gold forms numerous al-
loys and intermetallic compounds with many
metals and metalloids. The alloys have in most
cases face-centered cubic (fcc), hexagonal close
packed (hcp), or body centered cubic (bcc) crys-
tal structures, but there are also a great vari-
ety of different structure types, especially for
the intermetallic compounds. Gold forms con-
tinuous solid solutions with the fcc-crystallizing
22 Gold, Gold Alloys, and Gold Compounds
metals silver (atomic radius 144.5 pm), cop-
per (127.8 pm), platinum (137.3 pm), palladium
(137.6 pm), iron (124.1 pm), cobalt (125.3 pm),
and nickel (124.6 pm). The solid solutions are
generally of the substitutional type, where the
solute atoms replace atoms of the solvent atoms
in their lattice positions. Substitutional solid so-
lutions are only formed if the components have
the same or similar crystal structures and if the
atomic radii of solute and solvent do not dif-
fer by more than ca. 15 % (“size factor” after
Hume-Rothery [104]).
Figure 9. Solid solution hardening of gold [110]
Some systems show miscibility gaps, which
in combination with temperature-dependent de-
creasing mutual solubility are used for precipi-
tation hardening.
Alloying with elements with other lattice
structures or larger differences in atomic radii
like the hexagonal-crystallizing metals zinc
(atomic radius 133.5 pm), cadmium (148.9 pm),
or mercury (150.3 pm) results in the formation
of more complex structures.
In some of these alloy systems, structural
ordering reactions occur with the formation
of superlattices of the same or similar lattice
types. Such transformations are accompanied by
changes in the mechanical and physical prop-
erties which find application in the hardening
of the corresponding gold alloys. Superlattices,
formed by disorder – order reactions are found
in gold alloys with components which show
marked differences to gold in their electrochem-
ical properties or in their atomic sizes. Typical
compositions have atomic ratios between 3 : 1
and 1 : 3, or 2 : 1 and 1 : 1 (e.g., Au3Cu, AuCu3,
Au3Pd, Au3Cd, Au3Zn, Au2Mn, AuCu, AuMn)
[105, p. 636]. The ordered phases form in cer-
tain temperature ranges superstructures with al-
ternating regular linear arrangement of periods
of definite lengths, which meet in the crystal
at the so-called anti-phase boundaries (APBs).
The number of cells per period depends on
the valence-electron concentration and changes
with alloying element and composition [106].
Figure 10. Influence of alloying elements on the electrical
conductivity of gold [112]
Intermetallic compounds of gold with metals
of the A group and with the B group elements
of the periodic table form a variety of differ-
ent structures in dependence on the alloying el-
ements and the composition. Many of them are
stable over an extended composition range and
represent metallic phases rather than intermetal-
lic compounds of definite stoichiometric compo-
sition [107], [108].
Intermetallic compounds with B metals form
identical or similar crystal structures at
electron – to – atom ratios of 3/2, 21/13, and 7/4
 Gold, Gold Alloys, and Gold Compounds 23
Table 2. Hume-Rothery phases of Cu, Ag, Au

Electron: atom ratio = 3 : 2 Electron: atom Electron: atom ratio = 7 : 4

ratio = 21 : 13
Body-centered cubic Complex cubic Close-packed hexagonal “γ-brass” structure Close-packed hexagonal
structure (“β-manganese”) structure structure structure
CuBe Cu5 Si Cu3 Ga Cu5 Zn8 CuZn3
CuZn AgHg Cu5 Ge Cu5 Cd8 CuCd3
Cu3 Al Ag3 Al AgZn Cu5 Hg8 Cu3 Sn
Cu3 Ga Au3 Al AgCd Cu9 Al4 Cu3 Ge
Cu3 In Ag3 Al Cu9 Ga4 Cu3 Si
Cu5 Si Ag3 Ga Cu9 In4 AgZn3
Cu5 Sn Ag3 In Cu31 Si8 AgCd3
AgMg Ag5 Sn Cu31 Sn8 Ag3 Sn
AgZn Ag7 Sb Ag5 Zn8 Ag5 Al3
AgCd Au3 In Ag5 Cd8 AuZn3
Ag3 Al Au5 Sn Ag5 Hg8 AuCd3
Ag3 In Ag9 In4 Au3 Sn
AuMg Au5 Zn8 Au5 Al3
AuZn Au5 Cd8
AuCd Au9 In4

(Hume-Rothery phases) [97, p. 197]. Table 2
gives some examples.
Besides these, there are a huge number of
other intermetallic phases with predominantly
cubic, hexagonal, or tetragonal symmetry [36,
p. 502].
Influence of Alloying. Strengthening is per-
formed by alloying and by thermal treatment.
Hardening is effected either by solid solution
(causing elastic interactions between disloca-
tions and solute atoms), by precipitation hard-
ening using miscibility gaps, or by dispersion
hardening [109]. Figure 9 gives some examples
for the solution hardening effect of different
alloying elements [110]. Precipitation harden-
ing is of practical importance in jewelry, in
dentistry, and in industrial apparatus and con-
struction components. In binary and ternary
gold – copper and gold – copper – silver alloys
with higher copper contents, additional hard-
ening can be obtained by means of ordering
reactions [111]. Dispersion hardening is ef-
fected by incorporating in very fine distribu-
tion small amounts (0.1 – 2 vol %) of very small
particles of high-melting compounds (e.g., ox-
ides, carbides), which are insoluble or only be-
come soluble near the melting temperature of
the noble metal matrix. Dispersion strengthen-
ing is of importance if high electrical conduc-
tivity has to be combined with high-tempera-
ture mechanical strength and corrosion resis-
tance. Dispersion-hardened alloys are produced
by powder-metallurgical methods, supported by
milling of the mixed powders (mechanical al-
loying), by internal oxidation of the base metal
components in the alloy, or by precipitation of
the gold powder in the presence of refractory
oxides.
Fine grain structure is needed for reasons
of higher strength and forming characteris-
tic to give a smooth surface, especially in
jewelry and dentistry. Effective grain refining
for castings of gold and gold alloys is per-
formed by adding small amounts of iridium,
ruthenium, rhenium, zirconium, barium, tanta-
lum, niobium (0.01 – 0.1 %), or combinations of
Co/Ba, Co/Mo, Ni/Mo. Zirconium, barium, and
cobalt increase the recrystallization temperature
by about 150 – 200 ◦ C and suppress grain growth
on further annealing.
Figure 10 shows the influence of alloying ad-
ditions on the electrical conductivity [112]. The
increase in resistivity in the low concentration
range is proportional to the atomic concentra-
tion of the solute.
8.1. Binary Alloys [28], [98–102], [113]
The phase diagrams of some important binary
gold alloys are shown in Figures 11, 12, 13, 14,
15, 16, 17, 18, 19. The most frequently used bi-
nary alloys of gold are:
24 Gold, Gold Alloys, and Gold Compounds

Figure 11. Phase diagrams of groups 1 and 2 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Figure 12. Phase diagrams of groups 4 to 6 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Gold – Silver. Gold forms a continuous se-
ries of mixed crystals with silver, without
any transition or separation in the solid state.
Au – Ag 20 is used for low-voltage electrical
contacts, e.g., rivets.
[12006-51-8], and CuAu3 [12044-96-1] appear
in the solid state. Au – Cu alloys are also used
as highly oxidation resistant, high-temperature
stability alloys in turbines, nuclear, and space
technology, and jet engine components.

Gold – Copper. Gold – copper alloys solid-
ify as a continuous series of mixed crys-
tals, with a melting point minimum at 910 ◦ C
and ca. 20 wt % copper. Below 400 ◦ C, the
ordered phases Cu3 Au [60748-60-9], CuAu
Gold – Nickel. This continuous series of
mixed crystals, with a melting point minimum
at 950 ◦ C and ca. 18 wt % nickel, decomposes
at temperatures below 800 ◦ C into gold-rich and
nickel-rich mixed crystals. These alloys are used
 Gold, Gold Alloys, and Gold Compounds 25

Figure 13. Phase diagrams of groups 9 and 10 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Figure 14. Phase diagrams of groups 8 to 10 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Figure 15. Phase diagrams of group II binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

as brazing alloys; the most common composition
is Au – Ni18 wt %. It has high oxidation resis-
tance and good thermal stability up to 800 ◦ C.
The production of turbines, jet engines, and
components and devices in nuclear and space
technology are fields of application. Au – Co5
and Au – Ag26 – Ni3 serve as contact materials
which are resistant to silver migration.
Au alloys with small amounts (up to
1 – 3 wt %) of iron, cobalt, or nickel are elec-
trolytically deposited as hard, wear-resistant sur-
face coatings of electrical contacts.
Gold – Palladium. With palladium, gold
forms a continuous series of mixed crystals,
without any phase separation in the solid state.
Gold – Platinum. Gold mixes with platinum
in all proportions. Unlike the narrow melt-
ing range in gold – palladium alloys, most
gold – platinum alloys solidify within a very
26 Gold, Gold Alloys, and Gold Compounds

Figure 16. Phase diagrams of group 12 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Figure 17. Phase diagrams of group 13 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

broad temperature range. In the solid state, a
miscibility gap develops, which approaches the
solidus curve in the middle of the phase di-
agram. Because of their high corrosion resis-
tance, Au – Pt alloys are used for spinnerets
in rayon production, and also serve as high-
melting platinum solder. A typical composi-
tion is Au – Pt30 with a liquidus temperature of
1450 ◦ C and a solidus temperature of 1228 ◦ C.
Alloys with 40 – 65 wt % Au can be effectively
hardened by quenching from 1100 ◦ C and an-
nealing at ca. 500 ◦ C to a tensile strength at room
temperature up to ca. 1400 N/mm2 . Au – Pt10
and Au – Ag25 – Pt5 are used for electrical con-
tacts operating under highly corrosive condi-
tions. Au – Cu14 – Pt9 – Ag4 is used for oxide-
free slip contacts of high reliability at very low
voltage and current.
 Gold, Gold Alloys, and Gold Compounds 27

Figure 18. Phase diagrams of group 14 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Figure 19. Phase diagrams of group 15 binary gold alloys (upper abscissas in wt %, lower abscissas in atom %)

Gold – Zinc. With zinc, gold forms mixed
crystals to a limited extent. The phase diagram
for this system is very complex, and shows a
large number of intermetallic phases and transi-
tions in the solid state.
Gold – Cadmium. The characteristics of this
system are very similar to those of gold – zinc.
Gold – Titanium. The alloy Au – Ti1 wt %
has become important in the field of bonding
wire for the connection of bond pads of semi-
conductor chips of intergrated circuits to the
outer leads. Thermomechanical treatment ef-
fects strengthening by forming the intermetal-
lic compound Au4Ti. Additional hardening can
be performed by dispersion hardening by pro-
longed heating at elevated temperatures in air,
which effects the formation of finely dispersed
titanium oxide particles by internal oxidation of
the titanium containing component [114].
28 Gold, Gold Alloys, and Gold Compounds

Au – Si, Au – Ge, Au – Sn. The alloy sys-
tems gold – silicon, gold – germanium, and
gold – tin form low-melting eutectics (AuSi3,
1 wt %: mp 370 ◦ C, AuGe 12 wt %: mp 356 ◦ C,
AuSn 20 wt %: mp 280 ◦ C). They are of high
strength and serve as corrosion resistant and
mechanically stable solders in the fabrication of
semiconductor devices.
dental materials are complex because they must
have specific properties.
The ternary alloys of gold are industrially
more important than the binary alloys and have
been thoroughly investigated and documented.

Gold – Mercury. Up to a gold content of ca.

10 %, these alloys are liquid at room tempera-
ture. For higher gold contents, many intermetal-
lic compounds occur. Room temperature is usu-
ally sufficient for the formation of gold amal-
gams, which are still used in the recovery of
gold.
The phase diagrams for most of the remain-
ing systems, including those which are not used
in industry, have also been thoroughly investi-
gated.

Figure 21. Brinell hardness of annealed and quenched

gold – silver – copper alloys

Figure 20. Gradation of color of gold – silver – copper al-

loys

Figure 22. Corrosion resistance of gold – silver – copper al-

8.2. Ternary Alloys [103]
For centuries, the color (Fig. 20), hardness
(Fig. 21), and corrosion resistance (Fig. 22)
of gold were modified by variations in the
Au – Ag – Cu system. When white gold, with its
resemblance to platinum, became fashionable at
the beginning of this century, Ni and Pd were
added; these were soon followed by Zn, and later
by platinum. The gold alloys used for modern
loys
a) Alloys are tarnish resistant and resist all acids except
hydrochloric acid in the presence of an oxidizing agent;
b) Acids may dissolve out copper and silver from the sur-
face of the alloy; c) Alloys tarnish and are attacked by acids
Gold – Silver – Copper. Figure 23 shows the
liquidus, and Figure 24 shows isothermal sec-
tions through the miscibility gap of the gold –
silver – copper system. The melting surface is
characterized by a gutter starting from the
 Gold, Gold Alloys, and Gold Compounds
silver – copper eutectic and continuing in the di-
rection of the melting point minimum of the
gold – copper system. As the temperature de-
creases, the miscibility gap at the silver – copper
binary edge broadens out considerably towards
the gold corner. Shortly after solidification, the
heterogeneous phase only extends to alloys con-
taining slightly more than 40 % gold; at 400 ◦ C,
it includes alloys with 75 % gold.
Figure 23. Liquidus of the gold – silver – copper system
Figure 24. Isothermal sections through the miscibility gap
of the Au – Ag – Cu system
The miscibility gap covers a large part of the
gold – silver – copper system, and its extent is
strongly dependent on the temperature. This is
of great significance in the processing and ap-
plication of gold alloys, and is the main reason
why age-hardening is possible.
29
Figure 25 shows a section through the phase
diagram of the gold – silver – copper system,
running from the gold corner to the middle of
the silver – copper edge. As the temperature de-
creases, the regions in which mixed crystals and
melt occur are followed by regions in which
gold-rich α mixed crystals, and the two mixed
crystals α1 (silver-rich) and α2 (copper-rich) co-
exist. The saturation line of the α mixed crystal,
which separates the two regions from each other,
is highly temperature dependent. At 750 ◦ C, the
α mixed crystal can dissolve ca. 50 % silver and
copper (in approximately the ratio 1 : 1); at ca.
300 ◦ C, it can only take up about 10 % silver and
10 % copper. An alloy with 70 % gold, which
at high temperatures consists only of α mixed
crystals, reaches the saturation line during cool-
ing at ca. 480 ◦ C. With further cooling, it splits
into the α1 and α2 mixed crystals. At tempering
temperatures below 480 ◦ C, the alloy therefore
age-hardens.
Figure 25. Section through the Au – Ag – Cu phase diagram
running from the Au corner to the middle of the Ag – Cu
edge
Figure 26 shows a section through the ternary
system parallel to the silver – copper binary edge
with a constant gold content of 70 %. The exten-
sive region of the α mixed crystals adjoins the
miscibility gap which ends just below 500 ◦ C.
In the miscibility gap region, the α1 mixed crys-
tal, which has a relatively high silver content,
and the α2 mixed crystal, which has a relatively
high copper content, coexist.
30 Gold, Gold Alloys, and Gold Compounds
Gold – Nickel – Copper. Figure 27
shows the liquidus isotherm of the
gold – nickel – copper system, which produces
white alloys over broad areas. Below 800 ◦ C
in the gold – nickel system (Fig. 14), a misci-
bility gap stretches far into the ternary system,
as the temperature falls, in the direction of the
copper corner. These alloys can therefore be
age-hardened, but are not always easy to pro-
cess, particularly as the nickel content makes
them very sensitive to traces of sulfur. As lit-
tle as 0.01 % sulfur is sufficient to make them
brittle when hot. Phase separation in nickel-con-
taining white gold alloys leads to the formation
of a gold-rich mixed crystal, and a nickel-rich
ferromagnetic phase, which tends to lower the
chemical resistance of the alloys.
Figure 26. Section through the Au – Ag – Cu phase diagram
parallel to the Ag – Cu edge with a constant gold content of
70 %
Gold – Silver – Palladium. Figure 28 shows
the liquidus isotherms of this system, which pro-
duces white, high-melting alloys over a broad
area. These are relatively soft and cannot be age-
hardened.
8.3. Higher Alloys
In jewelry, the most important quaternary al-
loys are derived from the ternary systems
Au – Ag – Cu, Au – Ni – Cu, and Au – Ag – Pd,
most often through the addition of zinc. The
Au – Pd – Ag – Cu and Au – Ni – Ag – Cu sys-
tems are also of practical importance. Colored
gold solders may contain cadmium in addition
to the above elements.
Dental gold alloys often have five or
more components. These are formed from
Au – Ag – Cu by addition of Pd and Pt.
Figure 27. Liquidus isotherms of the gold – nickel – copper
system
8.4. Production and Processing [115–117]
Manufacture. Bars, rods, foils, and wires
are manufactured by classical metallurgical pro-
cesses: melting, casting, rolling, drawing, and
powder-metallurgical compaction. Pure gold is
very malleable. It can be rolled to very thin
foils and drawn to wires of very small diam-
eters. Special procedures have been developed
for the production of gold leaf (see Section 10.9)
and for casting small jewelry items. Gold pow-
ders of different grain sizes and shapes are made
by precipitation from preferably aqueous solu-
tions of gold compounds with reducing agents.
Thicker, compact surface layers are produced by
cladding, especially for electrical contact pieces

and jewelry items (Doublé). Thin surface lay-
ers or films are produced by galvanic processes,
by application of gold-powder-containing paste
preparations, by evaporation, or by sputtering.
Metallizing pastes contain additions of organic
vehicles for flow properties. They are applied by
painting, by brushing or by screen printing, in the
latter case usually followed by drying and firing.
Special preparations differing in gold powder
grades and type of liquid components are in use
for the production of electronic devices. Pastes
for the production of so-called thick-film layers
on ceramic substrates may contain glass pow-
ders which effect in the firing operation bonding
on the ceramic surface.
Figure 28. Liquidus isotherms of
gold – silver – palladium system
Melting. Gold alloys are made by melting
fine metals in crucibles made of a clay – graphite
mixture or fireclay. Gas-heated furnaces used
to be common, but electrically heated smelting
plants or induction furnaces are now used. In or-
der to prevent oxidation of the base metal com-
ponents, the melt is covered with lumps of char-
coal and borax. The air above the crucible can
also be replaced by carbon dioxide. Melting is
sometimes carried out in vacuum. The molten
metal is poured into preheated iron molds to ob-
tain the required form.
Rolling and Drawing. Cast plates are flat
rolled to form sheets; billets are first shaped on
grooved rolls, and then drawn to form wires. In-
Gold, Gold Alloys, and Gold Compounds 31
termediate annealing processes are usually car-
ried out in electrically heated furnaces. In order
to prevent oxidation of gold alloys, a protective
gas consisting of partially burned coal gas or
propane is blown through the furnace.
Fabrication of Jewelry. In former times,
gold jewelry was made by hand from sheets
and wires, and the pieces soldered together. The
mechanical properties of the alloys were not crit-
ical because the goldsmith was able to adapt
his methods according to the material. With the
increase in factory production, quality require-
ments became much more important. The cor-
rect choice of a gold alloy for a particular pro-
duction process has thus become critical.
Beating, Deep-drawing, Spinning, and Press-
ing. Soft gold alloys are most suitable for these
methods. Moderately hard or soft gold alloys are
used to manufacture jewelry from sheet metal,
such as brooches and rings. Chains and plaits are
now almost exclusively machine-made; for this
purpose, all soft alloys, and a very few moder-
ately hard alloys can be used. Alloys for chains
must have constant mechanical and processing
properties, so that the machine can produce a
well soldered strand. For pin shanks, spring
catches, and other similar articles, the hardest
possible alloys must be used, because good re-
sistance to wear and high elasticity are required
[117].
Punching. To make seamless wedding rings,
a hole is punched out of a disk. The resulting
the piece then undergoes a heavy forming operation
without removing any material, in a specially
adapted production process.
Casting. The manufacture of jewelry by cast-
ing gold in molds made of metallic or inor-
ganic materials, or sometimes organic materi-
als (cuttlebone), has been used throughout his-
tory. The casting of jewelry using the lost wax
process has become an important manufacturing
method. Several wax models of the desired shape
are made in a split mold, provided with a joint
gate, and embedded in a paste mixed with wa-
ter, consisting essentially of quartz and gypsum.
When this paste has hardened, the wax is melted
out, and the hollow mold fired at red heat. The
molten gold alloy is then poured in. After cool-
ing, the formed pieces are removed, smoothed,
and polished.
32 Gold, Gold Alloys, and Gold Compounds
Age-Hardening. The hardness of many
gold – silver – copper alloys can be increased by
heat treatment at 250 – 350 ◦ C. However, in the
fabrication of jewelry only limited use has been
made of this possibility, because the hardening
that takes place during forming is usually suffi-
cient.
As age-hardening in gold – silver – copper al-
loys takes place at lower temperatures than re-
covery after cold forming, the superposition of
age-hardening and forming operations can lead
to a considerable increase in the hardness and
strength of a workpiece. This method is useful
in the fabrication of parts which are to serve as
holding or fixing elements.
9. Quality Specifications and
Analysis [20], [118–124]
9.1. Quality Specifications [39]
The gold content of fine gold and gold al-
loys is usually expressed in fineness (parts per
thousand) or in carat, where 24 carat repre-
sent 1000/1000 (
) fine, 18 carat thus being
equal to 750/1000 (Table 3). For ores, inter-
mediate industrial products, residues and waste
materials, the gold content is usually given in
gram per metric ton (g/t), µg/g, ounces per met-
ric ton (oz/t) or ounces per short ton, where
1 oz = 1 troy ounce = 31.1035 g and 1 short
ton = 907.184 kg. Other mass units are 1 dwt = 1
pennyweight = 0.05 oz = 1.555 g and 1 troy
grain = 1/24 dwt = 0.0648 g. 1 tola = 11.664 g is
an Indian mass unit for gold. The Chinese Gold
and Silver Exchange Society uses the unit tael
(1 tael = 37.429 g).
Gold bars are classified into two “qualities”,
depending on their method of manufacture: cast
and struck. For the accredited refiners 38 differ-
ent bar masses ranging from 12.5 kg to 1 g are
recorded [125].
In international gold trading the content of
gold is the decisive criterion. The concentrations
of individual impurities are normally not taken
into consideration if their sum does not exceed
the specified upper limit. If agreed upon, the
ASTM Standard Specification for Refined Gold
(ASTM: B 562-95) can be used as a guideline
for the chemical composition. Individual refin-
ers may offer different specifications based on
their own products. ISO 9202 lists the fineness of
gold jewelry alloys, which constitute the mayor
use of refined gold. Special industrial applica-
tions of gold may require particular specifica-
tions for individual metallic or nonmetallic trace
elements.
9.2. Sampling [119], [126]
An essential part of any determination of the
gold content of any material and of great eco-
nomic significance is sampling before analysis.
A number of partly automated standard sam-
pling procedures are available for solid materials
that can be homogenized by comminution and
mixing (ores, concentrates, sweeps, and others),
and for unrefined gold and gold alloys that can
be homogenized by inductive melting. Where
these approaches are not possible, homogeniza-
tion by, for example, dilution melting with cop-
per or other base metals may be necessary.
Grindable materials are usually screened af-
ter grinding to separate the fine from the (metal-
lic) coarse fraction. These are then subjected
separately to mechanical, electrothermal, or
manual sampling processes.
In the case of metallic materials such as
mined gold, doré silver, or industrial gold al-
loys, the material to be analyzed can be obtained
by sawing sample bars or by drilling or sawing
small dip samples (buttons).
For the sampling of jewelry alloys, an ISO
procedure is being worked on at present [127].
Recycled electronic material contains mostly
only a few parts per thousand gold together with
plastic and base metal or ceramic components.
In a multistage process, mechanical size reduc-
tion in a shredder in combination with fractiona-
tion by screening produces material from which
samples can be taken [128].
9.3. Qualitative and Semiquantitative
Analysis
For the determination of gold, a large number
of spectroscopic methods, like FAAS, GFAAS,
ICP-OES, and XRF is available. In emission and
absorption spectroscopy the most sensitive lines
at 242.8 nm and 267.6 nm are used. To detect
gold in the µg/g range in powdered materials, fire
assay with lead as collector (see Section 9.4) can
 Gold, Gold Alloys, and Gold Compounds 33
Table 3. Fine gold specifications

Designation Gold Content of other

content, metals, µg/g
wt %

“Good delivery” gold ≥ 99.5 any metals (total)

≤ 5000
Fine gold ≥ 99.99 Ag ≤ 100
Cu ≤ 20
others ≤ 30
total ≤ 100
Fine gold, chemically ≥ 99.995 Ag ≤ 25
pure others ≤ 25
total ≤ 50
Fine gold, high purity ≥ 99.999 Ag ≤ 3
Fe ≤ 3
Bi ≤ 2
Al ≤ 0.5
Cu ≤ 0.5
Ni ≤ 0.5
Pd + Pt ≤ 5.0
total ≤ 10

be applied, in which silver nitrate, containing
less than 1 ng/g gold, is added to the fluxing
material, in order to improve the collector ef-
fect, and as protection against gold losses dur-
ing cupellation. The resulting bead can be dis-
solved in nitric or sulfuric acid, gold traces col-
lected on a membrane filter, dissolved in aqua
regia, and semiquantitatively determined spec-
troanalytically. Occasionally, the formation of
so-called purple of Cassius [124] is used as rapid
industrial procedure for the semiquantitative de-
tection of gold in tailing solutions from gold ex-
traction.
9.4. Quantitative Analysis
Quantitative analysis forms the basis for cal-
culating the gold content of all types of ma-
terials containing gold during its primary and
secondary extraction. The first group includes,
for instance, gold ores, concentrates, and mined
gold, while the second represents recovery from
scrap dental and jewelry alloys, doré silver, ion-
exchange resins, spent galvanic baths, electronic
scrap, and byproducts of the base metal indus-
try, such as sludges from copper electrolysis, etc.
Quantitative analysis is also used for quality con-
trol of the end products of refining ranging from
commercial gold to ultrapure gold and all the
products (e.g., alloys, and salts) obtained when
gold products are processed.
The duality of the methods for analyzing gold
for most of the materials mentioned is especially
characteristic, that is, the parallel use of classi-
cal and modern instrumental methods. The most
important analysis method for gold is still the
centuries-old docimastic analysis or docimacy
(Greek: testing, assay), more commonly known
as the fire assay. In this process, precious met-
als are taken up by molten lead while base met-
als are removed by slagging. Two variations of
the method are used to extract the gold from a
mainly nonmetallic or base metal matrix. In the
crucible assay, a mixture of lead oxide, a reduc-
ing agent (e.g. carbon), and a flux is melted at ca.
1300 ◦ C. In the scorification assay, the sample
is subjected to oxidative smelting with granu-
lated lead and borax at ca. 1000 ◦ C. In each case
a lead button containing the gold and the other
precious metals of the sample is formed.
The lead is then oxidized at ca. 900 ◦ C to
litharge (PbO) on a magnesia support known
as a cupel (cupellation process). The PbO melt
is absorbed by the porous magnesia (together
with base-metal oxides possibly present) and a
drop of precious metal(s), which later solidifies
to a bead remains behind. The precious metal
bead is treated with nitric acid. Depending on
the silver/gold ratio in the sample material, it
may be necessary to inquart the precious metal
34 Gold, Gold Alloys, and Gold Compounds
bead with additional silver to facilitate quanti-
tative separation of silver and gold during part-
ing. If the precious metal bead consists of Au,
Ag, Pt, and Pd in suitable concentration ranges,
Ag, Pt, and Pd are dissolved with boiling ni-
tric acid, while gold remains undissolved and
can be weighed. Cupellation losses are compen-
sated for by the use of proof samples of similar
composition to the material being assayed.
If the precious metal bead contains rarer
platinum group metals (Rh, Ir, Ru) in addition
to gold then special decomposition techniques
have to be applied.
An important alternative to the extraction of
gold and other precious metals with lead is the
use of copper as collector.
The cupellation of metallic samples, wrapped
in lead with an addition of silver, is the most im-
portant method for the accurate determination of
gold in alloys with ca. 30 to 99.9 % gold, e.g.,
dental alloys or mined gold [129]. The degree of
accuracy of gold analysis of alloys by cupella-
tion lies between about 0.1
and 1
depend-
ing on the gold concentration and the composi-
tion of the matrix.
Spectrometric methods with a precision
much better than 1 % are acceptable as alter-
natives to fire assay for the accurate analysis
of gold in the range from 0.1 % to the high-
percentage region. Up to the late 1980s this was
only true for wavelength and energy dispersive
X-ray fluorescence analysis (XRF) of solid al-
loys or solutions, and to a limited extent for glow
discharge optical emission spectrometry (GD-
OES) of gold alloys [130], [131]. With the X-
ray solution method as a multielement method
for all precious metals except Ag, an accuracy of
1
can be achieved for the analysis of gold as
main constituent [132], [133]. A small energy
dispersive X-ray instrument [135] allows gold
determinations in carat alloys with an accuracy
of 2 to 3
.
The basis for the precision analysis of pre-
cious metals by inductively coupled plasma op-
tical emission spectrometry (ICP-OES) is inter-
nal standardization. The essential method char-
acteristics for the determination of gold [134]
are
– The use of a simultaneous spectrometer with
high measurement stability
– The simultaneous measurement of the
267.6 nm or the 242.8 nm Au atomic line and
the 371.0 nm ionic line of yttrium as internal
standard
– The preparation of all solutions and the ad-
dition of the Y standard solution by exact
weighing
– In special cases the use of a Na/Cu buffer, but
in any case the use of a HCl concentration of
at least 5 %.
Several wet chemical/gravimetric methods
are used in special cases in conventional gold
analysis, for instance, reduction of gold by SO2
in hydrochloric acid solution.
9.5. Purity Analysis [121]
A large number of methods for purity analysis
of gold are available; some of them can be ap-
plied to metallic gold, and others to the analysis
of gold dissolved in acid.
9.5.1. Direct Analysis of Metallic Gold
1) Spark discharge emission spectrometry (SD-
OES) with high-speed time resolution of in-
dividual sparks is well suited for the analysis
of fine gold with total impurities in the range
of 50 to 1000 µg/g, that is, for the most com-
mon grades of fine gold in routine operation;
however, it is not suitable for 99.999 % gold.
2) DC arc spectrometry with simultaneous
background correction offered by the appli-
cation of a solid state detector (CID). The de-
tection limits for all trace elements are lower
than for spark excitation.
3) Spark ablation ICP-OES offers a further pos-
sibility of direct impurity analysis in which
sample ablation is caused by high-voltage
sparks and the resulting aerosol is trans-
ported into the ICP by an argon carrier gas
stream.
4) Glow discharge emission (GD-OES) or ab-
lation spectrometry (GDA-AAS). The detec-
tion limits for impurities in gold with clas-
sical DC-powered GD-OES are equal to or
better than 1 µg/g.
5) Laser ablation ICP mass spectrometry can be
applied to purity analysis in high purity gold
with detection limits of better than 0.2 µg/g.
 Gold, Gold Alloys, and Gold Compounds 35
Table 4. Coinage alloys

Coin Country Mintage period Fineness Carat Gross weight, g Gold

content
20 mark German Reich 1871 – 1915 900 21.6 7.964 7.168 g
10 mark German Reich 1871 – 1915 900 21.6 3.982 3.584 g
5 mark German Reich 1871 – 1915 900 21.6 1.991 1.792 g
1 ducat German
Confederation up to 1871 986.1 23.7 3.490 3.441 g
Krugerrand ∗ R. South Afr. since 1967 916.6 22 33.931 1 oz
Maple Leaf ∗ Canada since 1979 999.9 24 31.103 1 oz
American Eagle ∗ USA since 1986 916.6 22 33.931 1 oz
Britannia ∗ Great Brit. since 1987 916.6 22 33.931 1 oz
Nugget ∗ Australia since 1987 999.9 24 31.103 1 oz
Tscherwonez USSR since 1975 900 21.6 8.60 7.74 g

∗ Also in 1/2, 1/4 and 1/10 oz gold.

It has also found an interesting application in – Graphite furnace atomic absorption

the characterization of trace element com-
position of unrefined gold of different ori-
gins, akin to traditional fingerprinting. The
method therefore facilitates identification of
the provenance of stolen gold.
6) Glow discharge mass spectrometry GD-MS)
is the queen among spectroscopic techniques
for the analysis of gold of quality 99.995 %
Au or better; it is used in the electronics in-
dustry.
9.5.2. Purity of Gold Solution
As an independent alternative method to direct
metal analysis ICP-OES with a SIM/SEQU or
sequence instrument with axial plasma can be
used for production control or for the analysis
of gold calibration standards. The use of an Au
concentration of 50 g/L offers no difficulties. Es-
pecially advantageous is the use of ICP spec-
trometers with semiconductor detectors.
(GFAAS)
– X-ray fluorescence analysis with totally re-
flected exciting beam (TXRF)
– Direct current plasma optical emission spec-
trometry (DCP-OES)
– Inductively coupled plasma emission (ICP-
OES)
– ICP quadrupole mass spectrometry (ICP-
MS)
The gold traces may need to be enriched prior
to determination to improve the detection limits,
for instance, by solvent extraction. In the field of
trace analysis, composite fire assay/atomic spec-
troscopy or mass spectrometric methods play an
important role. They make use of the almost uni-
versal application of fire assay for the separation
of gold and the possible of using large samples.
10. Uses of Gold and Gold Alloys [6],
[12], [19], [20], [22], [35], [39], [45], [47],
[136], [137]

9.6. Trace Analysis 10.1. Coins, Medals, and Bars [138]

The determination of trace amounts of gold (ca.
0.1 – 100 µg/g) is important in ore prospecting
and in the evaluation of residues and waste ma-
terials from the metallurgical industry.
The solids can be dissolved and the result-
ing solution analyzed by a suitable spectroscopic
method:
– Flame atomic absorption (FAAS)
In antiquity, gold was considered an object of
value and used as a means of exchange, at first
in the form of nuggets or flattened disks, and
from 650 b.c. as minted coins. The composition
of the metal used varied from alloys containing a
high proportion of gold, to electrum which had a
relatively high silver content. The confusing va-
riety of gold coins, and the great variation in fine
36 Gold, Gold Alloys, and Gold Compounds
gold content, was first limited in the 19th cen-
tury, when legal regulations were introduced for
coinage, which specified nominal values of gold
coins, their weight, and gold content. After the
First World War, gold coins were no longer legal
tender. They are now traded as collectors’ items
and as a form of investment. With the liberaliza-
tion of private gold trading in the 1950s, the de-
mand for gold increased. A successful new enter-
prise in this market was the minting and market-
ing of the krugerrand (gold content of 1 oz troy)
by the Republic of South Africa. Between 1967
and 1985, a total of 2000 t (ca. 65×106 oz.) were
sold. Following the repressive measures which
have been inflicted on the krugerrand, new coins
were introduced by other countries (Table 4).
Gold was already stored in the form of bars in
antiquity, especially in Rome. Today, gold bars
weighing ca. 400 oz. (ca. 12 kg) of good delivery
quality (99.5 %) are the main form used in public
and institutional investment. Gross weight, gold
content, the manufacturing firm and reference
number are stamped on the bars, and provide di-
rect and binding information as to their value.
Smaller gold bars are manufactured for private
investors.
The difference between the buying and sell-
ing price in banks (broker’s commission) is nor-
mally ca. 3 – 4 % plus value added tax.
10.2. Jewelry [139]
Fine Content of Jewelry Gold. The gold
value of jewelry alloys is determined by their
gold content (fineness, cf. Section 9.1). In most
countries, laws govern the terms used in desig-
nating the fineness of gold jewelry for manufac-
turers, processors, and dealers.
Only alloys with a minimum gold content
of 585/000 are sufficiently tarnish resistant for
jewelry. Better quality jewelry customarily has a
gold content of 750/000. These alloys offer op-
timum color and mechanical properties. For less
expensive jewelry, alloys with a low gold con-
tent are often used. In Germany, 333/000 fine is
common, in other countries 375/000, and in the
United States 417/000. These alloys tarnish un-
der unfavorable conditions, and cracks may form
as a result of stress corrosion. The highest grade
alloys are used only occasionally in the manufac-
ture of jewelry, due to their low strength. How-
ever, no alloy can match the fine color of pure
gold.
Colored gold alloys used in the jewelry in-
dustry are mostly based on the ternary alloy sys-
tem Au – Ag – Cu, Cu or the quaternary system
Au – Ag – Cu – Zn allowing a wide variety of
colors (see Fig. 20). The workability and resis-
tance to wear of an alloy depend on its mechan-
ical properties; these, its resistance to corrosion,
and the color can be controlled by adding zinc.
The classification ranges for colored gold al-
loys used in the jewelry sector are shown in Ta-
ble 5. To designate the different qualities, spe-
cial codes are used, most of which are specific
to particular firms. The properties cover a broad
range of values to meet all practical requirements
(Tab. 6). In 1966 in the Federal Republic of Ger-
many, an industrial standard, DIN 8238 “Gold
colors” (including white gold), was created to
standardize colors in gold alloys and to provide
manufacturers with a better means of mutual un-
derstanding. This standard closely reflects sim-
ilar specifications in Switzerland and France. A
combination of values representing tone (T), sat-
uration level (S), and darkness (D), measured
using spectrophotometric methods, is attributed
to each color (Tab. 7).
Table 5. Composition of gold alloys for jewelry
Gold Content of alloy components, wt %
content,
wt %
Colored gold
22 carat 91.66 Ag 0 – 6.0, Cu 2 – 8.3
18 carat 75 Ag 0 – 20, Cu 5 – 25
14 carat 58.5 Ag 0 – 41.5, Cu 0 – 33.5, Zn 0 – 10
9 carat 37.5 Ag 0 – 56.0, Cu 4 – 60, Zn 0 – 15
8 carat 33.3 Ag 0 – 58.5, Cu 4 – 60, Zn 0 – 15
White gold
18 carat 76 Cu 4 – 8, Ni 10 – 18, Zn 3 – 6
18 carat 75 Pd 10 – 20, Ag 0 – 1, rest Cu, Zn
14 carat 59 Cu 15 – 25, Ni 10 – 16, Zn 5 – 8
14 carat 59 Pd 10 – 20, Ag 10 – 30, rest Cu, Zn
Gold Solders. The most frequently used
method of making joins in the manufacture of
jewelry from gold alloys is hard soldering. In ad-
dition to fine gold, colored gold solders also con-
tain silver, cadmium, copper, zinc, and indium.
Their melting temperature is always lower than
that of the material to be soldered. The additives
are adjusted so that the solders have graduated
 Gold, Gold Alloys, and Gold Compounds 37
Table 6. Properties and applications of jewelry gold alloys (selection)

Destignation Melting Density Vickers hardness Applications

Carat gold/silver, Color range, ◦ C g/cm3 (after soft
rest copper annealing), HV 10 1 2 3 4 5 6 7 8 9
or (+Zn)

Colored gold

18ct 750/40 red 880 – 900 15.1 160 hard X X X

750/90 reddish 870 – 890 15.3 150 medium hard X X X X X X X
750/125(130) yellow 850 – 890 15.4 140 medium hard X X X X X X X X
750/150(160) pale yellow 890 – 920 15.5 130 medium hard X X X X X X X X
750/200 pale yellow 900 – 970 15.8 90 soft X

14ct 585/40 reddish 900 – 920 13.0 130 X X X X X X X

585/45 yellow 835 – 860 13.0 100 X X X X X X
(+Zn)
585/100 reddish 820 – 870 13.3 140 X X X X
yellow
585/200 yellow 830 – 850 13.6 170 X
585/260 pale yellow 830 – 850 13.7 160 X X X X
585/300 pale yellow 820 – 890 13.9 140 X X X X X X X
585/340 green yellow 860 – 940 14.0 120 X X X X X X X
585/415 green yellow 1015 – 1020 14.3 50 X

9ct 375/90 reddish 870 – 930 11.2 120 X X X X

375/60 yellow 870 – 950 11.0 95 X X X X
375/150 pale yellow 770 – 860 10.9 140 X X X X X

8ct 333/90 reddish 890 – 930 10.9 110 X X X X

333/75 yellow 850 – 910 10.9 105 X X X X
333/120 pale yellow 800 – 860 10.5 100 X X X X X

White Gold

18ct 760S whitish gray 1000 – 1160 16.0 100 X X X X X

(contain Pd)
750M yellowish 1040 – 1150 15.8 140 X X X X X X
(contain Pd) white
760H1 white 920 – 960 14.9 210 X X X
(contain Ni)
14ct 590S whitish gray 1040 – 1130 14.5 90 X X X X X
(contain Pd)
590M yellowish 1060 – 1150 14.5 160 X X X X X X
(contain Pd) white
590H1 white 910 – 990 12.7 150 X X X
(contain Ni)
1 Rings, brooches; 2 Deep pulling work; 3 Pressing work; 4 Enamelling; 5 Castings; 6 Chains, lattice work; 7 Blanks for
minting; 8 Wedding rings; 9 Pipes, seamless.

Table 7. Gold colors according to DIN 8238

Symbol German classification Swiss and French Colorimetric measures according to DIN Examples of
classification 6164 approximately
corresponding gold
alloys
T S D

N weiß 1.2 0.9 1.6 590 H

8N grüngelb 24.8 1.6 1.2 585/17 340
1N blassgelb jaune pâle 1.7 1.7 1.2 585/260
2N hellgelb jaune pâle 1.8 1.8 1.3 750/160 (750/150)
3N gelb jaune 2.0 1.8 1.3 750/125 (750/130)
4N rosé rosé 2.4 1.6 1.4 750/90
5N rot rouge 2.6 1.5 1.4 750/40
38 Gold, Gold Alloys, and Gold Compounds
working temperatures. Three solders are gener-
ally sufficient, with graduations of ca. 50 ◦ C in
their working temperatures. Some examples of
colored gold solders are given in Tables 8 and 9.
White gold alloys were first developed in
the early 1900s, in an effort to replace platinum
by a cheaper material with identical properties.
White gold also differs from colored gold in hav-
ing a higher melting range (white gold with pal-
ladium) and is usually harder (white gold with
nickel). Nickel and palladium are the only suit-
able additives to give gold a color approaching
whitish gray. Because of the allergic reaction of
skin to Ni the demand for white gold has rapidly
fallen. Information about white gold alloys is
given in Table 5.
Table 8. Working temperatures of Cd-containing colored gold sol-
ders
Gold content, carat Solder designation
(Degussa)
18 750 L1
750 L2
750 L3
14 585 L1
585 L2
585 L3
9 375 L3
8 333 L1
333 L3
Table 9. Working temperatures of Cd-free solders
Gold content, carat Designation (Degussa)
14 585 L1 cdf
585 L3 cdf
18 750 L1 cdf
750 L2 cdf
750 L3 cdf
10.3. Electronics and Electrical
Engineering [22, pp. 475 – 500], [140], [141]
10.3.1. Electronics
The great advantage of gold is its high resistance
to oxidation and corrosion, and its high conduc-
tivity which give it excellent contact properties.
It is therefore primarily used if oxide-free
surfaces are indispensable. Gold surfaces en-
able the formation of electrical connections with
lowest ohmic resistances, forming perfect elec-
trical connections for solder, bond, and pres-
sure contacts where even thinnest oxide layers
would cause interruptions, formation of voids,
and leakages. It is used in active components
(diodes, transistors, integrated circuits, semi-
conductor memories), assembly and connec-
tion engineering (packages, thick-film circuits,
printed boards, and plugs) and, to a lesser ex-
tent, for passive components (capacitors and re-
sistors).
Table 10 gives a survey of the main applica-
tion fields.
Partly due to its high intrinsic cost, it is mostly
employed in the form of thin layers on different
substrate materials.
The gold used in electronics, with the excep-
tion of gold solders, is practically always fine
gold of purity 99.99 or 99.999 %.
The surface coats are deposited by electro-
Working
temperature,
plating [142], sputtering, evaporation, or by
◦ means of paste preparations, which are made
C
820 from special gold powder grades and organic
750 binders and – for adhesion on ceramic sub-
700 strates – blended with glass frits. These are ap-
780
720
plied by screen printing and firing. They are
670 especially used for conductor layers of hybrid
650 thick-film circuits and ceramic devices. Gold
700
conductor paths, pure or alloyed with silver, pal-
640
ladium, and platinum in thick-film circuits and
in submicron-structure units can also be made by
thermal decomposition by electron-beam lithog-
Working raphy.
temperature,
◦
Gold-plated surfaces serve for connections
C
by pressure, by bond – or solder – contacts on
800 semiconductor chips and for the joining of the
730
820 semiconductor pieces with assembling parts and
780 package components [143]. Gold conducting
750 layers are specially of importance in highly reli-
able electronic circuits, where silver conductor
layers may cause problems by current-induced
silver-ion migration.
Gold powder of different grain sizes with
spherical or platelike grain shapes are used in
metallizing and thick-film pastes to produce
bond pads and conductor layers. Gold powder,
as needed for paste preparations is produced by
the chemical reduction of tetrachloroauric acid
H[AuCl4 ]. Depending on the type of reducing
agent and the use of protecting organic colloids,
either spherical particles (with sizes between
1 µm and 10 µm) or platelike particles (with
 Gold, Gold Alloys, and Gold Compounds 39
Table 10. Application of gold and gold alloys in electronics , p. 557[36]

Bulk Bimetal Surface Coat

electroplated sputtered or pastes, lacquers solder connection

evaporated
bonding wires for plug-in contacts PCBs, plug-in thin film hybrid thick film hybrid special solders for
integrated circuits contacts, solderable circuits, conductor circuits, solderable die-attach, package
transistors, diodes and bond surfaces, contact, bond surfaces areas for contacts, soldering, and
switches, corrosion die-attach, IC connections in
protection of technology semiconductor power
semiconductor device devices
packages

Figure 29. Gold powder with platelet-shaped particles (0.5 – 50 µm) made by chemical reduction of an aqueous solution with
special additives [157, p. 57]

thickness of about 0.5 µm and flat dimensions
of about 50 µm; see Fig. 29) are formed.
Thin wires (“bond wire”, standard diameter
25 µm) made of pure gold, alloyed with small
amounts (ca. 7 ppm) of beryllium serve for the
connection of the majority of monolithic inte-
grated semiconductor chips (I/Cs) with the in-
ner leads of the device. Bonding is performed by
special welding processes (thermocompression
and thermosonic bonding), forming a bond loop
between the connection pads and the outer leads
of the device. The wire is fed through a heated
capillary and the tip of the outcoming wire is
melted to a small ball, which is pressed onto the
semiconductor pad to form a weld contact (ball
bonding or nailhead bonding, Fig. 30).
Bonding wire made of the alloy AuTi 1 has
higher strength and higher mechanical stabil-
ity at elevated temperatures. Strengthening is
achieved by thermal treatment which causes
the precipitation of the intermetallic compound
TiAu4 . Additional dispersion hardening can be
achieved by internal oxidation to form a finely
dispersed titanium oxide phase in the alloy struc-
ture [114].
Gold-containing brazing and solder alloys are
used for the joining of packaging and for the
assembly of components. The eutectic alloys
of gold with silicon, germanium, and tin (Ta-
ble 11) are used for low-temperature solder con-
nections with high mechanical strength. Gold
and gold – silicon alloys are used to connect the
semiconductor crystals with the base contact
40 Gold, Gold Alloys, and Gold Compounds
Table 11. Low-melting gold solder alloys for electronic applications , p. 556[22]

Composition Melting range, ◦ C Elongation, % Thermal expansion, Electrical resistivity, Thermal conductivity,
10−6 K−1 Ω mm2 m−1 W m−1 K−1
AuSn20 280 <1 16 > 0.2 57.3
AuGe12 356 <1 13.4 0.14 44.4
AuSi2 363 – 740 0.5 – 3 ∗ 12.6 0.031 50

∗ Hard-rolled condition.

supports (die-attach) on lead frames, packages, mal and mechanical stress and are therefore
or hybrid circuits. preferably applied in high-reliability semicon-
ductor devices submitted to thermal cycling.
AuGe12 and Au70In20Sn10 can be soldered at
400 – 500 ◦ C. They are used for the soldering of
Mo supports in power devices, packages, and
components and leads of Cu and FeCoNi alloys.
Ternary solder alloys of AuAgGe, AgCuSn
and AgCuIn of different compositions cover
the temperature range of 400 – 650 ◦ C. Some of
these are brittle and must be applied in powder
or paste form.

Figure 30. Ball bonding of semiconductor chips with gold Figure 31. Flat pack ceramic package for integrated circuit
bond wire [36, p. 561] devices with gold contact frame (with connections in dual
inline array). Hermetic encapsulation by soldering of gold
Gold-plated metallic lids and solder preforms plated metal lid with AuSn20 solder frame.
of the alloy AuSn20 are used for the hermetic
Nanosized gold particles have potential ap-
(vacuum-tight) sealing of semiconductor device
plications in electronics, computing, sensors,
packages (Fig. 31) and for soldering of laser
and catalysis. On the nanometric scale, materi-
crystals. AuSn alloy connections are also formed
als properties are strongly size dependent. Mas-
by thermal bonding of Sn-plated leads onto Au
sive gold clusters, which consist of 1 – 2 nm
bumps, placed on the surface of the semicon-
sized gold cores encapsulated within a shell of
ductor crystal with the tape-automated-bonding
tightly packed hydrocarbon chains have been
(TAB) technology [144]. AuSi alloys give sol-
prepared by decomposition of gold thiolate com-
der bonds with the highest stability against ther-
 Gold, Gold Alloys, and Gold Compounds
pounds. The electromagnetic and conduction
properties of these cluster molecules are ex-
tremely sensitive to charging and are of po-
tential interest for use in microelectronic cir-
cuitry (“single electronics”) [145–149]. Vapor-
synthesis techniques have been used to prepare
solvent-stabilized gold particles in the 1 – 3 nm
regime. The clusters may provide active cata-
lysts for the low-temperature oxidation of CO
to CO2 [150], [151]. Long “wires” of gold nano
particles have been deposited along step edges
of highly oriented pyrolytic graphite. The tech-
nique is supposed to perform in this way the
connection between components in a nanoscale
electrical circuit [152]. Spacing of nanoparticles
of gold has been also performed by attaching sin-
gle stranded DNA oligonucleotides of defined
length and sequence to the nanoparticles [153],
[154], [155].
10.3.2. Electrical Engineering [22,
pp. 449 – 459]
Because of its high oxidation resistance, gold
surfaces enable the formation of electrical con-
nections with the lowest ohmic resistances. The
surface layers are made by roll-bond cladding
or electrodeposition. Gold and gold alloys are
indispensable for conductor material and low-
voltage contacts for communication and infor-
mation transfer equipment, where even very thin
oxide layers would cause interruptions or fail-
ures in signal transfer.
Gold – nickel and gold – silver alloys are used
in weak-current engineering, as contact materi-
als for very low voltage switches, and where the
contact forces are low (relays, plugs, measuring
instruments). Micromigration of these alloys is
very low, and there is little tendency for insulat-
ing layers to form.
AuCr2 serves as resistor material in corro-
sive environments with stable temperature co-
efficient of resistance (TCR) between − 20 and
+ 40 ◦ C.
Wires of multicomponents alloys based on
gold and palladium serve as potentiometer wind-
ings in high precision techniques, where the low-
est TCR values in particular temperature ranges
are needed.
41
Gold-manganese alloys are used for
wirewound resistance thermometers. The
thermocouples Cu + Au 99,4/Co 0,6 and
Pt 90/Ir 10 + Au 60/Pd 40 are suitable for the
temperature ranges 0 to − 240 ◦ C and 0 to
700 ◦ C, respectively; the gold alloys form the
negative leg. Au – Ag – Cu-alloys are used as
surface material in sliding contacts.
10.4. Solders [22, pp. 492, 561 – 562], [156],
[157, pp. 157 – 163]
A variety of gold-based solder alloys are used in
the fields of apparatus technology, electronics,
jewelry, and dentistry.
Certain types of apparatus have compo-
nents made of iron and nickel alloys which
have to withstand high vacuums and high tem-
peratures. To join these materials, vacuum
hard solders are used, made of either fine
gold, or gold – copper, gold – silver – copper,
gold – nickel, gold – copper – nickel, and
gold – palladium alloys. Soldering is carried
out in a vacuum furnace or in a protective gas
(hydrogen, cracked gas).
Hard silver solder is normally used to
join stainless steels. However, if these joints
do not exhibit sufficient corrosion resistance,
gold – nickel – zinc alloys similar to white gold,
with ca. 80 % gold, 15 % nickel, and 5 % zinc,
are occasionally used.
In the fabrication of electronic devices,
gold based alloys of the composition gold – tin
(25 wt % Sn, mp 280 ◦ C), gold – silicon
(3.1 wt % Si, mp 370 ◦ C), and gold – germanium
(12 wt % Ge, mp 356 ◦ C) are used.
They allow soldering at relatively low tem-
peratures and give connections of high mechan-
ical strength, good corrosion resistance and ther-
mal conductivity (see also Section 10.3.1).
In jewelry, individual chain links, setting for
stones, and hollow-ware parts are soldered with
solder alloys which must correspond in cartage,
color, and mechanical properties to the materi-
als to be joined, but have melting temperatures
that are sufficiently lower to avoid melting of the
noble metal pieces [158]. These solder and braz-
ing alloys are principally of the same or similar
composition to the metal parts to be joined. For
42 Gold, Gold Alloys, and Gold Compounds
consecutive solder operation, alloys with differ-
ent melting temperatures (first, second, third sol-
ders) are applied.
Gold-based solder alloys are used in den-
tistry to join prosthetic dental pieces. Alterna-
tive methods are microplasma welding and laser
welding. The solder alloys are of similar com-
positions to the dental alloys. They must cor-
respond to the base materials in their corro-
sion behavior and thermal expansion. Solders
for crowns and bridges melt in the temperature
range of around 760 – 840 ◦ C. They are based on
the Au – Ag – Cu system with additions of zinc
and tin. Melting is usually done by gas torch.
Solders for PFM alloys (see also → Dental Ma-
terials, Chap. 2.3.) are used before porcelain ve-
neering. The melting temperatures and softening
ranges must be sufficiently high so that subse-
quent baking does not influence the mechanical
stability of the solder joint. These solders are
based on the Au – Ag system with reduced pal-
ladium and platinum content. Color lightening
is effected by palladium additions, and the melt-
ing temperatures are adjusted by additions of tin,
indium, or zinc [159].
Joining of gold and gold alloys at consider-
ably lower temperatures can be performed by
using diffusion processes, for instance by using
tin foil between components of pure gold and
heating the assembly above the melting point of
tin but below the melting temperature of gold
[160].
10.5. Pen Nibs
Nibs for fountain pens are usually made from
Au – Ag – Cu yellow gold alloys which are rel-
atively hard; occasionally white gold alloys are
also used. The alloys must be able to withstand
the very corrosive ferro-gallic inks; only 14 or
18 carat alloys are suitable. The nib points must
be made of hard metal alloys, which usually con-
tain Ru, Os, Ir, W, or Co.
Nibs made of stainless, ink-resistant nickel
chromium steel are sometimes coated with a thin
layer of gold; however, this does not improve
their ink resistance.
10.6. Chemical Technology [161]
Gold – platinum alloys containing 50 – 70 %
gold, which can be age-hardened, are used to
make spinnerets used in the production of man-
made fibers. Their fine-grained structure is of
great advantage in making the necessary fine
holes (diameter 25 – 120 µm).
Gold alloys are sometimes used for seals and
rupture disks that come into contact with corro-
sive substances. A gold – silver – palladium al-
loy (Pallacid) containing 30 % gold and 30 %
palladium is resistant to strong mineral acids,
is considerably cheaper than gold, and also has
greater high-temperature strength.
A gold alloy containing 10 % platinum is
used to make crucibles for analytical laborato-
ries, e.g., for ash determination of flour and other
phosphorus-containing foods. Unlike platinum
crucibles, it is resistant to corrosion by phos-
phorus compounds when red-hot.
10.7. Dental Materials
Gold alloys are of great importance in prosthetic
dentistry, for restorations such as gold fillings,
crowns, bridges, cast dentures, clasps, anchor-
age pins, and metal frameworks for dental ce-
ramics (→ Dental Materials). These materials
have to meet a number of requirements. They
must be resistant to normal conditions in the
mouth, of a suitable color, of different strengths,
and be easy to work. Today almost all alloys used
are of a complex composition, containing high
proportions of gold, palladium, and platinum. In
the past few years the number of components is
decreasing because of allergenic problems. The
advantage of these alloys mainly lies in their very
fine-grained and homogeneous structure.
10.8. Coatings [162–168]
10.8.1. Electroplating and Electroforming
The technical and decorative properties of gold
can be combined with a variety of cheap sub-
strates by applying a thin layer of gold to base
metals, ceramics, glass, or plastics.
 Gold, Gold Alloys, and Gold Compounds
Electroplating is by far the most frequently
used method (→ Electrochemical and Chemical
Deposition, Chap. 8.9.). Modern gold electro-
plating is mainly gold alloy plating for the fol-
lowing reasons:
1) For the adjustment of color. Gold alloys can
be deposited in a variety of shades. For exam-
ple, co-deposition of copper gives a reddish
color, nickel a white color, and cadmium a
yellow color. Colors of gold alloys are stan-
dardized in DIN 5033 and DIN EN 28 654.
2) To improve hardness and wear resistance.
3) In gold alloy deposits part of the gold is re-
placed by alloying elements which in most
cases have a lower density. Thus, substantial
savings of gold may be achieved.
Gold coatings are deposited mainly from
solutions of potassium dicyanoaurate(I),
K[Au(CN)2 ]. There are three groups of plat-
ing solutions:
1) Alkaline cyanide electrolytes, which enable
the dissolution of Cu, Ag, Cd and other metal
salts and their co-deposition with gold.
2) Neutral electrolytes have been developed for
lower carat deposits and higher thicknesses.
These electrolytes are also used for pure gold
deposits with high thicknesses.
3) Acidic electrolytes (pH 3 – 5) for produc-
ing high-carat deposits with properties re-
quired by the electronics industry and also
for decorative purposes. These electrolytes
are based on the finding that solutions of
K[Au(CN)2 ] are stable at a pH value as
low as 3.2. Deposits can be hardened by co-
deposition of elements such as Ni, Co, or Fe.
An electrolyte based on the cyanide com-
plex of trivalent gold, K[Au(CN)4 ] has been dis-
closed. The electrolyte is operated at low pH
(0.2 – 1.5) and is suitable for difficult-to-plate
metals, e.g., stainless steels [164].
Non-cyanide electrolytes contain gold
mostly as the sulfito complex [Au(SO3 )2 ]3− .
These plating solutions have a very good throw-
ing power and result in bright crack-free thick
deposits with excellent ductility. However, wear
resistance is poor. The main drawback of the
sulfite electrolytes is the instability of the solu-
tion.
Properties of gold coatings which are rele-
vant to their applications are: color, brightness,
43
hardness, wear resistance, porosity, and corro-
sion resistance. Gold and gold alloy coatings
are produced in a wide range of thicknesses
(0,1 – 200 µm), depending upon their applica-
tion.
Electroless or autocatalytic gold-plating so-
lutions usually contain potassium dicyanoau-
rate(I) together with a reducing agent such
as sodium hypophosphite, sodium borohydride,
or dimethylamine borane (DMAB). Electroless
gold plating is used only where electrolytic pro-
cesses cannot be used. Typical fields of applica-
tion are the electronics industry, e.g., in printed
circuit boards and in semiconductor electronics
[165].
Electroforming (→ Electrochemical and
Chemical Deposition) has been defined as “the
production or reproduction by electrodeposition
of an article on a mandrel or mold, that is subse-
quently separated from the deposit”. Gold up to
a thickness of 0.2 mm is deposited on a mandrel,
which is then removed. Wax mandrels can be
melted out. A self-supporting gold layer is left
which can be reinforced by a filler material. A
process for depositing 8-, 9-, 14-, or 18-carat
gold – silver alloy coatings has been developed
[166], [167]. The process of electroforming is
also used for manufacturing high-technology
equipment [168].
Table 12. Classification of precious metal preparations
Appearance Consistency
liquid/pasty solid
glossy bright gold
bright lemon gold
bright palladium
bright platinum
lusters
matt burnish gold dusting gold
burnish palladium dusting white gold
burnish platinum dusting silver
10.8.2. Bright Gold
Ceramic materials, especially high-quality
porcelain and glass, are often gilded by firing on
preparations of bright gold and burnish gold (Ta-
ble 12, see also → Ceramic Colorants). The es-
sential components of these lacquer-like paints
44 Gold, Gold Alloys, and Gold Compounds
are gold sulforesinates, mixed with natural oils
and resins. The preparations are applied mainly
either by hand or by screen printing processes.
Firing is carried out at 500 – 1250 ◦ C. Gold coat-
ings for technological applications also may be
applied by this method.
Precious metal (PM) preparations for the dec-
oration of ceramic (CerDecOr, dmc2 ) materials
are classified by:
– Consistency: liquid/pasty or solid
– Appearance: glossy or matt
– Precious metal content: gold, platinum, pal-
ladium or silver preparations.
Bright PM preparations are varnishlike or-
ganic compounds containing precious metals,
combined with flux components (based on or-
ganometallic compounds) as adhesion promot-
ers. These preparations also contain resin solu-
tions as film formers. After firing, a high-gloss
precious metal film forms on a smooth surface.
According to the color shade of the fired product,
a distinction is made between:
– Bright gold, which develops a typical red-
dish yellow gold shade after firing and con-
tains a small proportion of silver.
– Bright lemon gold, which fires to a lemon-
yellow shade, achieved by formation of an
gold – silver alloy.
– Bright platinum and bright palladium, which
fire to a white-gold shade, achieved by for-
mation of an Au – Pt or Au – Pd alloy.
Burnish PM preparations are varnishlike or-
ganic compounds containing precious metals
combined with flux components based on or-
ganic metal compounds. The flux compounds
promote adhesion, and resin solutions as film
formers. A dull precious metal film is formed af-
ter firing, which develops a satin surface during
subsequent burnishing with a glass-fiber brush,
sand, or other compacting materials. Burnish
PM preparations are subdivided into:
– Burnish gold, which often contains a small
portion of silver in addition to gold, enabling
the color shade to be varied from reddish yel-
low to yellow to greenish yellow, depending
on the alloy.
– Burnish platinum and burnish palladium,
which fire to a white gold shade, achieved
by the formation of an Au – Pt or Au – Pd
alloy.
– Burnish silver, which is mainly used for the
decoration of gift articles and contain only
silver as its only precious metal.
To meet the requirements of differing produc-
tion techniques, two types of dusting PM prepa-
ration are available, which differ in their particle
morphology: leaf gold flakes consist of precious
metals or their alloys in form of very finely flaked
particles. Painter’s gold is a chemically precip-
itated, crystalline precious metal powder with
mostly spherical particles:
– Dusting gold has a typical reddish yellow
shade after firing. Preparations with yellow
shades can also produced by alloying with
silver.
– Dusting white gold achieves its color by al-
loying with platinum and/or palladium.
– Dusting silver contains silver which may be
modified with a slight fraction of gold.
Dusting PM preparations are primarily used
to produce high-grade decals. Decorations pro-
duced with dusting gold (leaf gold flakes), dust-
ing white gold, and dusting silver have a per-
manent attractive metallic appearance without
after-treatment. Decorations produced painter’s
gold (used to hand paint gold decorations) have
to be burnished. Dusting silver trends to tarnish
after some time.
Lusters are varnishlike preparations, based
on metal- and/or precious-metal-containing or-
ganic compounds, with resin solutions as film
formers. When fired on porcelain, earthenware,
enamel, tiles or glass they produce very thin,
intensively colored and lustrous layers, which
give them their metallic iridescent finish. They
are classified according to color shade, precious
metal content, and special effects, as indicated
by their classification as craquelling or marbling
lusters, running lusters, and halo lusters.
Table 13 lists the characteristics of different
preparation ranges.
The precious metal content influences mainly
the color of the preparations. The differentiation
within the range of bright preparations is sum-
marized in Table 14.
 Gold, Gold Alloys, and Gold Compounds 45
Table 13. Characteristics of different preparation ranges

Type of preparation Lustres Bright PMP Burnish PMP Matt PMP Dusting PMP
Parameter

Surface glossy, iridescent glossy matt after polishing matt without polishing semi matt
Condition of the liquid liquid partly solid partly solid solid
components
Stirring before use no no yes yes no
Gold content, % 0–6 6 – 15 16 – 40 9 – 15 80 – 100

Table 14. Colors of PM Preparations according to precious metal content

Color Au, % Ag, % Pd, % Pt, % Name

Reddish yellow 100 Bright Gold

Yellow 90 10 Bright Gold
Greenish yellow 70 30 Bright Lemon Gold
White 70 10 20 Bright Palladium
White 70 10 10 10 Bright Palladium

10.8.3. Other Gold Coatings 10.9. Gold Leaf

Rolled gold is still used for spectacle frames
and gold-plated watches. However, it has lost its
former significance in favor of electroplating.
Rolled gold is fabricated by soldering gold
sheets, usually 14 carat, to blocks made of cop-
per alloy or stainless steel. These are then rolled
or drawn to the desired shape, producing strips
and wires with a largely non-porous gold coat-
ing, usually 5 – 10 µm thick.
Fire Gilding. In this process, the part to be
gilded is painted with gold amalgam. The mer-
cury is evaporated by heating, leaving a rela-
tively thick gold layer. The process is very prob-
lematical with regard to industrial hygiene.
Vapor Deposition of Gold. To achieve a
sufficiently abrasion resistant coating of true
gold color, a base layer of TiN is applied which
is topped with less than 1 µm of gold [169]. In
microelectronics gold layers are deposited for
contacts or leads on hybrid ICs by sputtering
or evaporation. Sometimes architectural glass
is coated with gold instead of silver (reference
to low emissivity coatings with Ag in the Ag-
chapter). This combines the solar control func-
tion with a spectacular decorative effect. Heat
protection by thin gold layers also is used in
space technology, e.g., in space suits.
Gold leaf is usually made of fine gold or
Au – Ag – Cu alloys with a very high gold con-
tent. Thin foils are rolled in a package arrange-
ment. Production starts with sheets of about
20 µm thickness. These are placed between
sheets of vellum, beaten down, and finally ham-
mered by hand, using separating membranes
made of the cecum of cattle (“goldbeater skins”)
to a thickness of about 0.2 µm [170]. A modern
method of making gold leaf is cathode sputter-
ing.
The crystal plane (100) in beaten gold leaf lies
in the plane of the leaf. Gold leaf is used to gild
wooden statues, book edges, and fabric prints. In
certain beverages ( Danziger Goldwasser) foods,
it is used to achieve visual effects.
In former times, small rolls of gold leaf were
used to fill cavities in teeth.
10.10. Catalysts
Gold shows activity in both heterogeneous and
homogeneous catalysis.
Gold in platinum group metal and in silver-
based catalysts acts as promoter to effect higher
yields and higher selectivity. Hydroforming of
paraffins and cycloalkanes with gold-containing
iridium catalysts gives higher yields of aromatic
46 Gold, Gold Alloys, and Gold Compounds

compounds at temperatures above 500 ◦ C. An- 11. Economic Aspects [2], [4], [18–20],
other example is the acetoxylation of ethene to [39], [40], [47], [178–180]
form vinyl acetate over Pd – Au catalysts [171].
Supported active gold catalysts are obtained Production. Gold represents a significant
by coprecipitation or deposition precipitation of portion of the total world economy. In the Re-
gold from precursor compounds on to transition public of South Africa, it occupies in terms
metal oxides such as Mn2 O3 or Fe2 O3 . The op- of value the highest position among all indus-
timum conditions for functionality are gold par- trial goods. About 500 000 people are employed
ticle sizes of 2 – 5 nm, which may interact with worldwide in gold production 300 000 – 400 000
oxide support that can itself in some way par- of them in the Republic of South Africa. The
ticipate in the reaction [172]. They surpass the value of the gold from primary production in
activity of mercury catalysts for the hydrochlori- 1997 was about ¤ 20 × 109 . Thus it occupies
nation of ethyne and are especially suited for the third place in the metal trade, after pig iron
catalytic activated low-temperature oxidation of (¤ 100 × 109 ) and aluminum (¤ 23 × 109 ), and
carbon monoxide [173]. The method of copre- before copper (¤ 11 × 109 ) [178]. Global gold
cipitation, followed by aging of the gold con- mine production grew from 390 t in 1900 to
taining precipitate, which changes thereby from 2576 t in 1999 [178].
the amorphous to crystalline structure, is impor- At present, almost half of the gold obtained
tant for sustained high activity. from ores is produced in the Republic of South
Gold catalysts are also promising in both the Africa, The United States, Canada, and Aus-
selective and nonselective oxidation of hydro- tralia. Table 15 shows the primary production of
carbons, in the reduction of nitrogen oxides by gold in the various producer countries [179].
carbon monoxide, propene, or hydrogen, in the
hydrogenation of carbon oxides [172], and in
the epoxidation of propane with O2 /H2 mixtures
[174]. Table 15. Global mine production of Gold 1998 and 1999 in t [179]
Gold on carbon catalysts have been used for
Country 1998 1999
the selective liquid-phase oxidation of diols with
dioxygen in alkaline solution under mild con- South Africa 464 450
ditions (343 – 363 K). As with gold catalysts in United States 366 342
Australia 310 303
the gas phase, the gold particle size is important. Canada 164 158
Particle size was 7 nm, the catalyst was prepared China 160 156
by deposition precipitation from H[AuCl4 ] and Indonesia 139 155
sodium carbonate, followed by reduction with Russia 127 138
Peru 91 127
formaldehyde [175]. Uzbekistan 80 86
Homogeneous catalytic action is shown by Ghana 73 78
cationic gold(I) phosphine complexes in the ad- PNG 63 65
Brazil 55 54
dition of alcohols to alkynes. These gold cata- Chile 47 48
lysts are also significantly better than the pre- Argentina 20 35
viously used mercury catalysts and work under Philippines 35 32
mild conditions (20 – 50 ◦ C) in the presence of Zimbabwe 27 30
Mali 23 25
acidic co-catalysts [176], [177]. Mexico 26 23
Platinum vapor, which forms from Colombia 22 21
platinum – rhodium catalysts during the oxida- Kyrgyzstan 21 20
Rest of World 226 231
tion of ammonia to nitric acid can be retained by
a gold or gold – palladium gauze. This process Total 2541 2576
has long been in industrial use.
 Gold, Gold Alloys, and Gold Compounds
Supply and Demand. The supply of gold on
the market in 1997 was about 2700 t/a (Fig. 32).
Most of this (73 %) came from total world
mine production, 20 % came from recycling pro-
cesses, and 7 % was sold by the former Soviet
Union. Buying and selling on the part of gov-
ernment monetary authorities can have a strong
effect on the market; in recent years official sec-
tor sales have increased significantly.
Figure 33 shows the demand for gold accord-
ing to industrial applications.
Gold Trade. London is the most important
market for gold in terms of the quantity traded.
The London gold market has a fixing system,
whereby the price of gold is determined twice
daily, according to supply and demand, by re-
presentatives from five firms of brokers. This is
then published as the “fixing price”. The United
States futures markets have a strong influence
on the calculation of this price. The fixing price
serves as an orientation point for gold traders all
over the world.
Zurich is also an important center of the gold
trade. A considerable part of the gold from South
African primary production, which up to 1968
all went to London, is now sold to Zurich, as
well as most of the gold from the Soviet Union.
Another important center is New York. Other
metal exchanges, such as Hongkong, Frankfurt,
Paris, Singapore, and Tokyo, are of more re-
gional importance.
Gold is traded internationally in the form
of gold bars of various weights, and with a
gold content of 99.50 – 99.99 %. In London, gold
bullion must contain gold weighing between
350 and 430 oz; the commonest figure is about
400 oz (ca. 12 kg).
Important factors which influence the price of
gold are assessment of political circumstances,
inflation rates, and the rate of interest of the US
dollar as a key world currency. The huge gold
holdings of central banks and several central
bank disposals had been weighing on the price
of gold in 1997 and 1998 together with increas-
ing amounts of gold forward sales of producers.
On August 28, 1998, the price of gold was fixed
at $ 273.40 per ounce – at that time a fresh 19
year low.
47
12. Toxicology and Occupational
Health
Gold and its soluble compounds generally only
seldom cause acute or chronic problems in
the workplace and in the environment. Tetra-
chloroauric acid H[AuCl4 ] [16903-35-8] as is
a strong acid with corrosive effects on the skin.
Gold(III) salts are more poisonous than gold(I)
compounds. After intake of gold(III) chloride
lethal poisonings with toxic effects on liver
and kidneys are observed. Potassium dicyanoau-
rate K[Au(CN)2 ] [14265-59-3] liberates hydro-
cyanic acid, which can cause poisoning. Poison-
ings by high doses of other gold compounds are
also known [181], [182].
The daily intake of gold in food is estimated
at less than 7 µg. Usual concentrations in blood
are 15 µg/L [183] or over less than 0.5 µg/L, with
an average of 0.1 µg/L [184].
Gold Therapy. Gold compounds are used in
the treatment of chronic rheumatoid arthritis and
of pemphigus vulgaris in dermatology. A 30 %
incidence of side effects is known [185]. Thera-
peutic effects and toxicity correspond with water
solubility [186]. Medical treatment uses weakly
soluble gold(I) thiolates such as Myocrysin (dis-
odium gold(I) malate [42722-04-3]) or Solganol
or Aureotan (gold(I) thioglucose [12192-57-3]).
The drug is administered by intramuscular injec-
tion in relatively high doses. Toxic side effects
include cardiovascular disorders, nerve dysfunc-
tion and adverse effects on liver, stomach, and
bone marrow. Allergic effects occur on the skin,
mucous membranes, and, rarely, in the lungs.
The development of drug-induced lichen planus
is also possible [185].
A possible consequence of chronic gold ap-
plication is chrysiasis, a blue gray discoloration
of the skin, similar to argyria [185].
Gold Allergy. Skin allergies to gold jewelry
or dental gold have rarely been observed. In
many cases they could be attributed to less pre-
cious alloying elements such as nickel, cobalt,
or copper.
48 Gold, Gold Alloys, and Gold Compounds
Figure 32. Gold supply in 1997 (ca. 2700 t)
(source: Bericht der Degussa Ffm Edelmetallmärkte 1997)
Figure 33. Gold industrial demand in the world in 1997 (ca. 2750 t)
(source: Bericht der Degussa Ffm Edelmetallmärkte 1997)
13. References
1. Gmelin, System no. 62.
2. H. Quiring: Die metallischen Rohstoffe, 2nd
ed., vol. 3 “Gold,” Enke Verlag, Stuttgart 1953.
3. Degussa, Sol & Luna – auf den Spuren von
Gold und Silber, Frankfurt 1973.
4. B. Neumann: Die Metalle – Geschichte,
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The article contains sections titled:

1. Introduction
2. GMP in the USA
3. GMP in the EU
4. GMP in the Wider World
5. The ICH Q7A Guideline
6. Quality Management
7. Principal Requirements of GMP
7.1. Personnel
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7.4. Processes
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9. GMP in API Process Development

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1. Introduction
Good Manufacturing Practices (GMPs) represent the minimum requirements that must be satisfied when producing
pharmaceuticals for human or veterinary use [1]. They mandate a high degree of control over all stages of the
manufacturing process, from ordering the raw materials through to packaging and dispatching the finished goods. All
aspects of production must be described in written procedures, and all production activities must be thoroughly
documented as they are carried out.

GMPs may be viewed as the third element of a trio of “GXP” regulatory requirements, which comprise also Good
Laboratory Practice (GLP) and Good Clinical Practice (GCP). GLP mandates certain standards for laboratories engaged in
scientific studies of new drug candidates, e.g., to obtain toxicological or pharmacological data from studies on animals.
The GLP regulations enforced in the USA are detailed in part 58 of the Code of Federal Regulations Title 21. The
equivalent requirements in the European Union are covered in Section II of the annex to Council Directive 87/18/EEC,
amended by Commission Directive 1999/11/EC. GCP refers to basic principles in the conduct of clinical trials involving
human patients. Within Title 21 of the U.S. Code, these issues are dealt with in parts 50, 54, and 56. The EU is currently
harmonizing requirements for clinical trials across all its member states. A Clinical Trials Directive was published in the
Official Journal of the European Communities in May 2001, and all states are expected to be in compliance with this by
2004. GMP governs the actual manufacturing of drug substances and products; it is mandatory for the production of
clinical supplies of novel drugs and for commercial supplies of approved drugs.

This article will mainly focus on the GMP requirements at the stage of chemical manufacturing — the manufacturing of
“drug substances” or “active pharmaceutical ingredients” (APIs). The requirements for “drug products” — i.e., the dosage
forms such as tablets, capsules, injectable vials, etc — and for the manufacture of medical devices, are different and
generally more stringent, but these are not discussed in detail here.

One of the principle reasons for GMP is to ensure the consistency of drug manufacturing processes. It avoids the situation,
prevalent in other areas of the chemical industry, in which the final testing performed on individual batches or units is the

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main, or even the sole, determinant of product quality. Reliance on testing alone is not appropriate for pharmaceuticals
because:

Testing is only performed on a small sample, which may not be completely representative.
Defective products which escape detection at the testing stage constitute a grave danger to consumers (patients).
Patients themselves have no means of detecting such defects and cannot rectify them.

Testing cannot be relied upon to detect all failures in the manufacturing process; some defective batches will always get
through. In some situations, such as the manufacture of socks or compact discs, this may not be a serious concern, since
it causes only mild irritation to the 0.1 % (say) of customers who inadvertently purchase the defective objects, and they
then have the option of returning them to the shop. With pharmaceuticals, the consequences of 0.1 % of patients receiving
defective medicines are potentially far more serious. Therefore, GMP places as much emphasis on Quality Assurance —
preventing the failures in the first place — as on Quality Control [2].

Even under the most tightly-regulated GMP regime, manufacturing problems and failures still occur, so Quality Control is
still important. But under GMP, such failures should not simply be accepted as an unavoidable “act of God”. Rather they
should be thoroughly investigated to determine the underlying causes and to prevent their recurring. By gradually
eliminating the causes of failure, the incidence of failure should decline over time, and greater confidence in the
consistency of the process is generated.

Under GMP, manufacturers are also expected to embrace novel technologies as they emerge, where these offer
significant quality improvements. Examples are the use of more accurate engineering control systems, surface coating
materials which are easier to clean and sanitize, and more sensitive techniques for chemical analysis. It is not that
innovation must be embraced for its own sake; the cost of a novel measure must be considered in relation to the quality
improvement it brings. However, the industry “benchmark” standards do evolve over time, hence prevalent use of the
acronym cGMP (current GMP).

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2. GMP in the USA

GMPs first emerged as a legal requirement in the USA in 1962, following substantial amendments to the 1938 Food, Drug,
and Cosmetic Act, and since that time they have been enforced by the FDA (Food and Drug Administration) [3], [4]. The
GMP regulations are detailed in part 211 of the Code of Federal Regulations Title 21. The current version has been in
force since 1978, but FDA announced a major review of their GMP policy in 2002, which is expected to take about two
years. The 21CFR211 regulations are legally binding requirements for all pharmaceutical manufacturers in the USA; drugs
imported from other countries must also have been manufactured according to these standards.

Part 211 is divided into 11 subparts, covering the following:

A. General Provisions: Scope, Definitions.

B. Organization and Personnel: Responsibilities of quality control unit; Personnel qualifications; Personnel
responsibilities; Consultants.
C. Buildings and Facilities: Design and construction features; Lighting; Ventilation, air filtration, air heating and cooling;
Plumbing; Sewage and refuse; Washing and toilet facilities; Sanitation; Maintenance.
D. Equipment: Equipment design, size, and location; Equipment construction; Equipment cleaning and maintenance;
Automatic, mechanical, and electronic equipment; Filters.
E. Control of Components and Drug Product Containers and Closures: General requirements; Receipt and storage of
untested components, drug product containers, and closures; Testing and approval or rejection of components,
drug product containers, and closures; Use of approved components, drug product containers, and closures;
Retesting of approved components, drug product containers, and closures; Rejected components, drug product
containers, and closures; Drug product containers and closures.
F. Production and Process Controls: Written procedures; Deviations; Charge-in of components; Calculation of yield;
Equipment identification; Sampling and testing of in-process materials and drug products; Time limitations on
production; Control of microbiological contamination; Reprocessing.
G. Packaging and Labeling Control: Materials examination and usage criteria; Labeling issuance; Packaging and
labeling operations; Tamper-resistant packaging requirements for over-the-counter (OTC) human drug products;
Drug product inspection; Expiration dating.
H. Holding and Distribution: Warehousing procedures; Distribution procedures.
I. Laboratory Controls: General requirements; Testing and release for distribution; Stability testing; Special testing
requirements; Reserve samples; Laboratory animals; Penicillin contamination.
J. Records and Reports: General requirements; Equipment cleaning and use log; Component, drug product container,
closure, and labeling records; Master production and control records; Batch production and control records;
Production record review; Laboratory records; Distribution records; Complaint files.
K. Returned and Salvaged Drug Products: Returned drug products; Drug product salvaging.

In the mid 20th century FDA's enforcement activities concentrated mainly on secondary (dosage-form) manufacturing, and
indeed the GMP regulations [5] were drafted entirely from the drug-product perspective. However, technically the U.S.
legislation does not distinguish between drug products (dosage forms) and drug substances (APIs), and since the early
1980s FDA has increasingly emphasized the application of GMPs to API manufacturing also, using the 21CFR211
regulations as guidelines in their inspections of API plants. Initially, this was a source of much confusion and frustration
among API manufacturers, because the regulations fail to take account of the very different manufacturing environment
prevalent in API production plants, as opposed to pharmaceutical formulation plants. In practice, different inspectors had
widely different expectations of how far the drug product regulations could reasonably be applied.

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In 1987, FDA published their “Guide to Inspection of Bulk Pharmaceutical Chemicals” (revised 1991). But while this
provided manufacturers with some useful insights into FDA's principal areas of concern, it is purely an internal agency
document with no legal or regulatory status. Only in the late 1990s did official FDA Guidelines on APIs begin to emerge.
Two draft versions were produced in 1996 and 1998, and the final version was endorsed in 2001. This final version is
identical with the “Q7A Good Manufacturing Practice Guidance for Active Pharmaceutical Ingredients”, drafted by the
International Conference on Harmonization (ICH), and thus is relevant not just in the USA but throughout the world [6].

FDA is required by its statutes to inspect all drug manufacturing facilities for GMP compliance once every two years — not
just USA-based companies, but also foreign facilities where products are manufactured for export to the USA. Recently,
however, the true inspection rate has declined to nearer once every six years, and the agency has been seeking ways to
rationalize its inspectional work by concentrating on companies or areas of manufacturing which present the highest risks.
Where an inspection reveals that a firm is not following the GMP regulations, its products may be deemed to be
“adulterated”, regardless of whether or not they are physically contaminated or otherwise defective. Thus they may be
barred from entry to the USA, seized, or even destroyed. In extreme cases, criminal penalties may be applied to the
company and to individual company executives. In recent years fines of up to $500 million have been levied against
several companies for GMP violations. However, most violative practices are associated with drug products rather than
APIs.

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3. GMP in the EU
In Europe, responsibility for drug regulation is split between various bodies: some national, some supranational. Until the
1990s, each country was essentially autonomous, maintaining its own agencies for drug approvals and inspections. For
example, in the UK the Medicines Control Agency (MCA) fulfilled these functions. Each national agency operated
according to its own procedures. The situation changed in 1995 with the establishment of the European Agency for the
Evaluation of Medicinal Products (EMEA). EMEA now coordinates the approval process for new human and veterinary
drugs throughout the EU, but most of the work involved is still carried out by the individual national agencies, now following
centrally agreed procedures. In matters of GMP and inspections, a degree of international cooperation has existed for
much longer, in the form of the Pharmaceutical Inspection Convention (PIC). Originally established in 1970 under the
auspices of the European Free Trade Association (EFTA), it now comprises 24 (mostly European) countries who
recognize the validity of each other's drug inspection procedures, with the aim of cutting down on unnecessary
transnational inspections. Attempts have been made to agree mutual recognition procedures with the USA as well, but to
date — in spite of a Mutual Recognition Agreement concluded in 1997 — these have been unsuccessful.

The European approach to GMP has been different from the American experience, in that there has been less emphasis
on legislative enforcement. Rather, government inspectorates have sought to work in cooperation with manufacturers to
encourage improvement in quality standards, in contrast to the adversarial and “investigative” approach associated with
the FDA. The first GMP guide to be produced in the UK was published in 1971. Known as the “Orange Guide” after the
color of its cover, this was originally intended as a Code of Practice for pharmaceutical manufacturers. Similar codes
appeared in other European countries over the next few decades. From the late 1980s, the guidelines of the EEC, later the
EU, were published, and eventually superceded those of individual member states. The Orange Guide continues to be
published in the UK (latest edition 1997), but is now a straight reproduction of the European text [7].

The Orange Guide covers the same ground as the Part 211 regulations in the USA, but in a different order, and in
somewhat greater detail. It is divided into nine chapters coving the following topics:
One Quality management: Principle; Quality Assurance (QA); Good Manufacturing Practice (GMP) for medicinal
products; Quality Control (QC).
Two Personnel: Principle; General; Key personnel; Training; Personnel hygiene.
Three Premises and equipment: Principle; Premises; General Production area; Storage areas; Quality Control (QC)
areas; Ancillary areas; Equipment.
Four Documentation: Principle; General; Documents required; Specifications; Starting and packaging materials;
Intermediate and bulk products; Finished products; Manufacturing formula and processing instructions; Packaging
instructions; Batch processing records; Batch packaging records; Procedures and records for Receipt, Sampling,
Testing; Other.
Five Production: Principle; General; Prevention of cross-contamination in production; Validation; Starting materials;
Processing operations: intermediate and bulk products; Packaging materials; Packaging operations; Finished
products; Rejected, recovered and returned materials.
Six Quality Control: Principle; General; Good Quality Control Laboratory Practice; Documentation; Sampling; Testing.
Seven Contract manufacture and analysis: Principle; General; The Contract Giver; The Contract Acceptor; The Contract.
Eight Complaints and product recall: Principle; Complaints; Recalls.
Nine Self-inspection: Principle

Additionally, there are 14 annexes, dealing with: Manufacture of sterile medicinal products, Manufacture of biological
medicinal products for human use, Manufacture of radiopharmaceuticals, Manufacture of veterinary medicinal products
other than immunologicals, Manufacture of immunological veterinary medicinal products, Manufacture of medicinal gases,
Manufacture of herbal medicinal products, Sampling of starting and packaging materials, Manufacture of liquids, creams
and ointments, Manufacture of pressurized metered dose aerosol preparations for inhalation, Computerized systems, Use
of ionizing radiation in the manufacture of medicinal products, Manufacture of investigational medicinal products,
Manufacture of products derived from human blood or human plasma.

GMP only became a legal requirement for drug product manufacturing throughout the EU in 1992, 30 years after its

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imposition in the USA. At that time it did not strictly extend to API manufacturing, although API manufacturers were
increasingly encouraged to follow GMP principles, and inspectorates took an increasing interest in their activities. Only
with the ratification of the international Q7A guidelines in 2001 did APIs finally become officially regulated by European
law.

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4. GMP in the Wider World

The Q7A guideline is also official policy in Japan, the third main participant in the ICH process. Elsewhere in the world,
most developed countries (e.g., Australia, Canada) have their own GMP regulations, but where these affect APIs they are
rarely significantly different from Q7A. Developing countries have tended to adopt the guidelines from the WHO, which
represent basic minimum standards for local pharmaceutical manufacturing, but are not considered suitable for the export
of drugs elsewhere.

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5. The ICH Q7A Guideline

The International Conference on Harmonization (ICH) is a joint forum between representatives of the regulatory authorities
and the pharmaceutical industry from the USA, the EU, and Japan. It was established in 1990 with a remit to harmonize
the technical standards for the registration of pharmaceuticals across the world. The main themes which it addresses are
Quality, Safety, and Efficacy. Over the years it has developed many guidelines on matters such as impurities, residual
solvents, clinical safety studies, stability testing, analytical validation, quality of biotechnological products, and much more.
There has also been progress towards a “Common Technical Document” to serve as a new drug application format
throughout the world.

Although GMP is not strictly a drug registration issue, and so is slightly outside its main remit, ICH became interested in
this subject in the late 1990s. By this time, GMP standards for drug products were well advanced throughout the
developed world, but were only enforced for APIs in the USA. FDA had issued their first “Guidance for Industry” on API
manufacturing as a discussion draft in 1996, with a second draft appearing in 1998 after some consultation with industry
representatives. Simultaneously, guidelines were being developed by the Pharmaceutical Inspections Convention (PIC)
[8], the European Federation of Pharmaceutical Industries and Associations (EFPIA) [9] and the Pharmaceutical Research
Manufacturers of America (PhRMA) [10]. ICH adopted these frameworks as the basis for their Q7A international
guidelines, which first appeared in draft format in 2000, achieving final endorsement in 2001. Shortly thereafter, Q7A was
officially adopted by the regulatory authorities in the USA, Europe, and Japan.

In the USA, Q7A has the status of a guideline, rather than a legally enforceable regulation. It represents FDA's current
thinking on the subject and describes practices which will be acceptable to them. But conformance with the guideline
recommendations is not mandatory; companies may adopt alternative approaches if they can be justified as consistent
with the 21CFR211 regulations.

In any case, the guideline does not prescribe or recommend any specific measures, procedures, specifications, or
controls; the emphasis is rather on ensuring that companies establish these for themselves. The word “appropriate”
appears throughout, emphasizing that requirements and constraints may vary from one company to another. The guideline
sets out the goals to be attained, but recognizes that they may be reached by different pathways. Each company is
expected to define its own approaches and to demonstrate that these will succeed in meeting the prescribed goals.

The main topics covered by the Q7A Guideline are:

– Quality Management
– Personnel
– Buildings and Facilities
– Process Equipment
– Documentation and Records
– Materials Management
– Production and In-Process Controls
– Packing and Identification Labeling of APIs and Intermediates
– Storage and Distribution
– Laboratory Controls
– Validation
– Change Control
– Rejection and Re-Use of Materials
– Complaints and Recalls
– Contract Manufacturers and Laboratories
– Agents, Brokers, Traders, Distributors, Repackers and Relabelers.

There is also specific guidance for APIs manufactured by cell culture or fermentation and for APIs used in clinical trials.

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6. Quality Management
For an organization to be compliant with cGMP, the most fundamental requirement is to have an effective quality
management structure. Quality should be the responsibility of all persons involved in manufacturing, but the system must
be defined and overseen by an independent Quality Unit, which is separate from all production activities. The manager of
this Quality Unit should report to a senior level of the organizational hierarchy, and should not be subordinate to the
production manager. The quality unit should be involved in all quality-related matters, and should review and approve all
quality-related documents.

The quality unit should fulfill the functions of quality control (QC) and of quality assurance (QA), though these may be
organized as separate units if desired – depending on the size and structure of the company. The QC function normally
comprises the analytical work carried out to ensure that specifications are met — e.g. for raw material quality, equipment
cleanliness or air quality. QA has a more wide-ranging role and has been defined (in Q7A) as “the sum total of the
organized arrangements made with the object of ensuring that all APIs are of the quality required for their intended use
and that quality systems are maintained”. The quality unit should have defined responsibilities, as detailed in the
guidelines, including the responsibility to release or reject batches of the final APIs.

One important QU responsibility is to ensure that internal audits, or self-inspections, are regularly performed to determine
whether established procedures are being followed and whether the cGMP regulations and guidelines are being observed.
The audit findings and/or corrective actions should be documented and brought to the attention of responsible
management.

Regular quality-reviews of APIs should be conducted at least annually, comprising in-process control and test results,
batch failures, deviations, nonconformances, process or analytical changes, stability results, complaints, and returns. The
results of these reviews should be evaluated and an assessment made as to whether any corrective action is required.

The emphasis that GMP places on Quality Management invites comparison with international quality standards such as
ISO 9000, which offer much useful advice on the construction of a logical Quality System [11]. However, ISO 9000 is a
generic standard, intended to be applied throughout all areas of industry and commerce, and does not specifically address
the peculiar needs of the pharmaceutical industry. While it covers many of the same themes as GMP, such as the
emphasis on management responsibility, resource management, product and service realization, measurement, analysis,
and improvement, other important areas are missing, e.g., hygiene and sanitation requirements, which would not
necessarily be relevant in other branches of industry. Under ISO 9000 the requirement is mainly to have written policies
covering the relevant elements; it is left mainly to companies' own discretion what these policies should be. The GMP
Guidelines tend to be much more prescriptive. Thus ISO 9000 registration may be a useful starting point for a company to
achieve GMP status, but it is neither a necessary nor a sufficient condition.

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7. Principal Requirements of GMP

The full text of the Q7A guideline is freely available from the FDA website [12], so only a brief summary is presented here.
The main provisions can be divided into requirements for Personnel, Materials, Premises and Equipment, and Processes.

7.1. Personnel
Personnel are often the most significant source of variance in a process, and most failures can ultimately be traced to
human errors. A drug manufacturer should therefore employ an adequate number of personnel with the necessary
qualifications and practical experience to perform and/or supervise the required tasks. The structure of the company
should be set out clearly in an organization chart, and all personnel should have specific duties recorded in written job
descriptions. Training in the particular operations that the employee performs, and in the cGMP regulations that relate to
his/her function, should be conducted regularly by qualified instructors. Records of such training should be maintained, and
its effectiveness should be periodically assessed. Appropriate clean protective apparel should be provided, and staff
should practice good sanitation and health habits.

7.2. Materials
All process materials must be carefully controlled to ensure they are only used in those processes for which they have
been approved. This means maintaining proper storage facilities, where clear distinctions are made between materials
which are quarantined, approved, or rejected/returned. Appropriate specifications should be developed for all starting
materials, reagents, processing aids, solvents, water, and primary packaging materials, as well as for the final APIs and
key intermediates. Each individual batch or lot should be uniquely identified and evaluated against its specifications before
being approved for use in any process. The evaluation should normally be carried out by the quality unit; however, for
some of the earlier less critical manufacturing steps, it may be performed by production personnel, following QU-approved
procedures. All incoming materials should be sampled, and at least one identity test performed. In many cases it is
acceptable to rely on a supplier's Certificate of Analysis as evidence of the required quality, as long as confidence in that
supplier can be justified on the basis of a quality audit or other evaluation process and of satisfactory experience.
Randomly selected lots of all incoming materials should be subjected to full specification testing from time to time.
Whenever a material is used in a process, its lot number and the precise amount dispensed should be recorded on the
batch production record, so that all materials are traceable back to their original sources. Records should also be kept on
the disposition of each lot.

7.3. Buildings, Facilities, and Process Equipment

Buildings and facilities used in the manufacture of intermediates and APIs should be located, designed, and constructed to
facilitate cleaning, maintenance, and appropriate operations, and to minimize the potential for contamination. There should
be defined areas, or other control systems, for distinct operations such as receipt, sampling, quarantine, storage,

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processing, packaging, and laboratory activities. Adequate lighting should be provided in all areas. Adequate ventilation,
air filtration, and exhaust systems are required for those environments where the final API is isolated, dried, or packaged.
Such areas should have smooth, continuous, and impermeable surfaces, with no sharp corners. API processes should
ideally be physically segregated from one another; if this is not possible, then adequate procedures should be established
which prevent cross-contamination.

Utilities such as steam, gas, compressed air, heating, ventilation, and air-conditioning should be qualified and
appropriately monitored wherever they may affect product quality. Drawings for these systems should be available, and
appropriate operating limits should be established.

All processing equipment should be of appropriate design and adequate size, and suitably located for its intended use,
cleaning, sanitation, and maintenance. Any surfaces which directly contact the raw materials or products should be
constructed of unreactive materials which will not adversely affect the quality of the API (e.g., steel equipment may not be
appropriate for processing corrosive materials such as hydrochloride salts). All instruments should be regularly calibrated
to ensure they consistently operate within defined tolerances.

Critical equipment and facilities should be formally qualified to demonstrate their suitability for the required operations and
their conformance to predetermined specifications. Qualification will normally be conducted in different phases, beginning
with a Design Qualification (DQ), in which the manufacturer's designs, blueprints, and specifications are compared with the
user's own requirements to assess whether the basic concept will meet the defined process demands. Once the item has
been installed and commissioned, it should go through the Installation Qualification (IQ) stage, which is a checklist to
confirm that all the necessary functionality (switches, gauges, electrical connections, etc.) is present and of a suitable
standard. The next stage is an Operational Qualification (OQ), in which the equipment is set to work on a typical task or
process (usually employing inert materials), and details of its performance are collected and assessed. Finally, in the
Performance Qualification (PQ), a trial run of a real process is conducted. (This PQ may be performed as part of the
validation of that particular process.)

All equipment should be subject to a regime of planned preventative maintenance, to ensure that it continues to operate
within its specifications, and to detect and rectify any potential problems at an early stage before they cause any batch
failures.

In some cases it may be necessary to dedicate the equipment to particular processes, most notably for the production of
highly sensitizing products such as penicillins.

Equipment should normally be cleaned to a satisfactory standard after each individual batch to prevent cross-
contamination between batches and, most importantly, between different products. Equipment dedicated to one process or
used for a multibatch campaign of the same product may be cleaned less frequently, but this should be justified on a case-
by-case basis.

Companies are expected to establish their own cleanliness criteria based on an assessment of their own circumstances.
Normally the criteria will include the requirement for no visible residue on the equipment surface. Where the surface is not
completely accessible for visual inspection, some indirect means should be established, such as a rinse test or a swab
test, with defined residue limits. Such limits should be rational, practical, achievable, and verifiable. For example, some
companies operate on the 10 ppm principle, whereby limits are set to ensure that the following product cannot be
contaminated with more than 10 ppm of the previous product. Other companies set limits to ensure that the maximum daily
dose of the following product cannot be contaminated by more than 0.1 % of the minimum daily dose of the previous
product.

Cleaning after each process should be defined in written procedures, which should be validated to ensure that they
consistently achieve the defined standards. Cleaning validation involves identifying the areas of the equipment which are
most difficult to clean and demonstrating that they are in fact cleaned to the required standard over a number of
consecutive (usually three) runs. This may involve dismantling the equipment to some extent to reach otherwise
inaccessible areas. However, cleaning validation need only be performed on a “worst-case” basis, that is, on those
processes which are judged to present the greatest cleaning difficulties [13].

7.4. Processes
The production of each batch of API or intermediate should be closely documented to provide as complete a record as
possible of the circumstances of its manufacture. To ensure uniformity from batch to batch, master production instructions
should be prepared, dated, and signed by one person and independently checked, dated, and signed by another person in
the quality unit. The master instructions should give details of all process materials required, including packaging and
labeling, with their quality specifications and amounts. The major production equipment should be specified, along with
detailed production instructions, including sequences, allowable ranges for process parameters, sampling instructions, in-
process controls, time limits for completion of individual steps, and expected yield ranges at appropriate phases. Each
individual batch should conform as far as possible to these master instructions, with any deviations being recorded,
investigated, and evaluated.

Each individual batch production record should identify the operators and supervisors involved with the batch, record
equipment numbers, the dates and times of each critical operation, the lot numbers of each ingredient used and the
precise amounts dispensed, the actual results recorded for critical process parameters and in-process controls, actual
yields at appropriate phases, details of any process deviations, and results of release testing.

7.5. Process Validation

A formal validation is required for all operations determined to be critical to the quality and purity of the API [14]. Process
validation is often a very time consuming and laborious activity; therefore, many companies perform it only on the final

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synthetic steps, relying on quality control and other GMP measures to assure the quality of the earlier, less critical
intermediates. A written validation protocol should be established that specifies how the validation of a particular process
will be conducted. This should identify the critical product attributes of the API (e.g., analytical specifications, physical
form), and the critical process parameters (e.g., temperatures, stoichiometry) which may affect these attributes. For each
critical parameter a normal operating range, a proven acceptable range, and, where appropriate, edge of failure limits,
should be established. A series of consecutive validation runs (usually three) is then undertaken to establish that the
process consistently falls within the defined ranges for each parameter and that the product consistently meets its quality
specifications.

Validation studies should normally be completed before any commercial distribution of the API (Prospective Validation).
For most new drugs, FDA approval will be withheld until the agency is satisfied that an adequate validation has been
performed. In a minority of cases, an alternative approach (Concurrent Validation) may be more appropriate. For example,
if the drug already has marketing authorization, its sales may continue while the validation studies are underway.
(However, since validation has been a requirement since the late 1980s, there can be few drugs remaining in this
category.) Another case would be where batches are made very infrequently because of low demand; in this situation the
first batch may be approved and distributed before the validation is complete, the validation being resumed with the next
batch. Concurrent Validation may also be used to justify approval of a single batch where there has been a substantial
deviation from the established (validated) process. This would comprise detailed assessments of the impact of the
deviation coupled with extra analytical investigations to ensure the quality of the drug substance. A third approach
(Retrospective Validation) is mentioned in FDA guidelines, but increasingly discouraged. This involves no validation runs
as such, but rather a detailed review of a large number (20–30) of consecutive historical batches, including any which have
failed. This approach presupposes that sufficient details were collected at the time.

Once a process has been validated, strict controls must be enforced to prevent unauthorized changes. Any proposed
changes to the process should be formally evaluated for the effect they may have on the critical quality attributes of the
API. If a process change is judged to be major, i.e., it has the potential to influence the quality of the product, then its
introduction should be preceded by a revalidation of the process. Minor changes which are judged unlikely to affect
product quality may be implemented without formal revalidation, provided they give an equivalent input to the process. (For
example, if the starting material is obtained from a new supplier, it should meet the same qualitative and quantitative
specifications as that from the previous supplier.) Each process should be reviewed on a regular (perhaps annual) basis to
assess how far it has shifted since its last validation, and a judgment should be made as to whether revalidation is
required.

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8. Applicability of GMP
GMP is expected to apply not only to the final API, but also to intermediate stages of the synthesis. But a significant
regulatory burden is incurred by companies when lengthy syntheses are subject to regulatory review and GMP inspection.
How far back in the synthesis GMP should reach remains a “gray area”. FDA has accepted that it is unreasonable to apply
GMP concepts to the original progenitors of the API, which may have come from plants, mines, oil wells, or sea water.
However, “it is reasonable to expect GMP concepts to start to become applicable at that point where a starting material
enters a biological or chemical synthesis or series of processing steps where it is known that the end product will be a BPC
(Bulk Pharmaceutical Chemical)” [15].

A key issue is therefore the definition of the “starting materials” for each synthesis. According to the Q7A guideline, these
are materials which are “incorporated as a significant structural fragment into the structure of the API”. Starting materials
may be purchased from an external supplier or contract manufacturer, or manufactured in-house, and accepted on the
basis of conformance to an analytical specification; there is no requirement to observe GMP during their manufacture.
Thus it is in the API manufacturer's interest to define the starting materials as late in the synthesis as possible. In the past,
starting materials were normally expected to be commercially available substances with a variety of uses. Compounds
produced specifically for the API synthesis were regarded as intermediates, and therefore subject to GMP. In practice,
however, many such compounds were accepted by FDA as starting materials, after review on a case-by-case basis. The
official FDA criteria for a starting material were [16]:

It is a compound whose name, chemical structure, chemical and physical characteristics and properties, and
impurity profile are well-defined in the chemical literature, or
It is obtained by commonly known procedures (this applies principally to starting materials extracted from plants and
animals, and to semisynthetic antibiotics).

More recently, commentators have criticized the vagueness of these criteria. PhRMA [17] has suggested as an alternative
that a noncommercial substance should be regarded as a starting material if all of the following apply:

It is a significant structural fragment of the drug substance.

It has a well-characterized structure and well-defined purity profile (whether or not published in the open literature).
Specifications exist which ensure appropriate control over downstream processing and drug substance quality.
It is not the final intermediate, used in the step which generates the API molecule itself.

The argument is that the improvements in analytical technology over the past decade make it more reasonable to expect
the quality attributes for starting materials to be readily identified and controlled.

Once the starting materials have been defined, all subsequent synthetic steps should be carried out under GMP, but this
need not be at a uniform level:

page 7 of 9
Good Manufacturing Practices : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
“Although strict observance of GMPs, approaching or equaling those expected for finished drug products, may be
expected in some types of bulk processes, in most others it is neither feasible nor required to apply rigid controls during
the early processing steps. In all processes of this type, however, the requirements should be increasingly tightened
according to some reasonable rationale. At some logical processing step, usually well before the final finishing operation,
appropriate GMPs should be imposed and maintained throughout the remainder of the process.” [15].

For example, the production of a very early intermediate may not require the ultralow residue limits on equipment, the
process segregation, or the environmental control associated with the final step. While all intermediates should be
evaluated and approved before further processing, for the earlier steps this may be performed entirely within the
production department, whereas for the later steps the involvement of the quality unit is mandatory. All intermediates
should be tested, but for in situ intermediates, this may involve no more than an in-process control. It is not necessary to
set formal specifications for each intermediate; but companies should identify the critical stages of their syntheses at which
specifications would be appropriate. The final intermediate is normally regarded as a major watershed in the synthesis —
the point beyond which GMP controls should be significantly increased; here the specifications and tests should be nearly
as stringent as those applied to the final API itself.

[Top of Page]

9. GMP in API Process Development

Pharmaceutical companies conduct a substantial amount of research into potential new therapeutic agents. Most
candidate new drugs will never be marketed; they are rejected either for lack of safety, lack of efficacy, lack of
bioavailability, or insufficient improvement over existing therapies. Nonetheless, they are tested on human volunteers
before these decisions can be made. APIs intended for use in such clinical studies are expected to be produced according
to appropriate GMP standards.

(Note that where the clinical trial material is produced on a small scale in a laboratory, its manufacture should still be
subject to GMP, and not GLP. GLP relates to the conduct of laboratory studies, not to manufacturing on a laboratory
scale.)

The application of GMP at the early investigative stage often gives rise to practical difficulties. By their nature, clinical
investigations must be carried out before there has been time to develop the optimum manufacturing methods. One of the
key features of GMP is process consistency, but this is the hallmark of a relatively mature process, and so is an unrealistic
expectation during the development of that process. Often, the early studies use API prepared by the original discovery
synthesis, which would not be appropriate for later large-scale manufacturing. It is difficult to set specifications for the
starting materials or intermediates in the absence of long processing experience. Also, without validated analytical
methods, it is difficult to be sure what impurities are present in the API. In some cases it is difficult to reproduce the
physical form of the product on a consistent basis. Clinical APIs will normally be produced in chemical pilot plants, where
the reactors are used for numerous processes, often only on one or two occasions each. Thus it is difficult to develop the
validated cleaning methods which guarantee against cross-contamination.

There is therefore a need for much more process flexibility at the development stage than could be tolerated in commercial
production. There must be more reliance on case-wise scientific judgment than on immutable specifications. But this
increased flexibility is mitigated by the more detailed attention that can be given to the production of individual batches, the
use of more highly qualified and experienced personnel, the more extensive testing carried out, and the relatively small
number of patients involved in the studies.

The Q7A guideline recognizes that not all the controls it recommends are appropriate for the manufacture of clinical APIs,
and makes some broad recommendations in Section XIX. This theme has also been developed in greater detail by the API
Committee of CEFIC, the European Chemical Industries Council [18]. Their approach to GMP for API Development is
based on the following principles:

The product should be fit for its intended use, and the safety of any subject in the clinical trails should be
guaranteed.
All information relating to the quality of the product or process should be retrievable and reconstructable.
Quality must be built into the process — the earlier the better.
During the development of an API the GMP controls should increase.

During early development there may not even be a firm specification for the API itself. The principle generally observed is
that its quality should be at least as good — and preferably better — than that used in the preclinical toxicology studies or
previous clinical studies. In particular it should contain no new impurities which were not present in those previous
batches.

GMP lays particular emphasis on the importance of good record keeping, and if anything this is even more vital in the early
project stages (when processes are changing rapidly) than during commercial operations (when the processes are largely
fixed). Information generated from the beginning of the project should therefore be constantly documented in development
reports. These allow the project to develop in a logical scientific manner, and facilitate the validation of the process when it
moves into commercial manufacturing.

But while it is necessary to exercise flexibility with process control issues during API development, there is no reason to be
less stringent in areas such as housekeeping, cleanliness, record keeping, equipment maintenance, calibration or staff
training. In these areas the standards in the pilot plant should be similar to those observed in a commercial API plant.

[Top of Page]

page 8 of 9
Good Manufacturing Practices : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

References
1. P. Uys: Good Manufacturing Practice. A Guide to Practical Quality Management, Sigma Press, Pretoria 1994.
2. K. McCormack: Quality, Butterworth-Heinnemann Pharmaceutical Engineering Series 2002.
3. I. R. Berry, D. Harpaz (eds): Validation of Active Pharmaceutical Ingredients, 2nd ed., IHS Health Group, Englewood,
CO 2001.
4. B. K. Immel: “A Brief History of the GMPs for Pharmaceuticals”, Pharm. Technol. 25 (2001) no. 7, 44 – 52.
5. Current Good Manufacturing Practice for Finished Pharmaceuticals, US Code of Federal Regulations, 21CFR Part
211, 1997
6. Food & Drug Administration: Guidance for Industry: Q7A Good Manufacturing Practice Guidance for Active
Pharmaceutical Ingredients, Rockville, MD 2001.
7. UK Medicines Control Agency: Rules and Guidance for Pharmaceutical Manufacturers and Distributors, The
Stationery Office, London 1997.
8. Pharmaceutical Inspections Convention: Regulations on the Manufacture of Pharmaceutical Active Ingredients (2/87),
1987.
9. European Chemical Industry Council & European Federation of Pharmaceutical Industries' Associations: Good
Manufacturing Practices for Active Ingredient Manufacturers, Brussels 1996.
10. Quality Control Bulk Pharmaceuticals Workgroup, PhRMA, Pharm. Technol., Dec. 1995, Jan. 1996.
11. ISO 9000: 2000: Quality Management Systems – Requirements, ISO, Geneva 2000.
12. http://www.fda.gov/cder
13. Food & Drug Administration: Guide to Inspections Validation of Cleaning Processes, Rockville, MD 1993.
14. Food & Drug Administration: Guideline on Principles of Process Validation, Rockville, MD 1987.
15. Food & Drug Administration: Guide to Inspection of Bulk Pharmaceutical Chemicals, Rockville, MD 1991.
16. Food & Drug Administration: Guideline for Submitting Supporting Documentation in Drug Applications for the
Manufacture of Drug Substances, Rockville, MD 1987.
17. T. Cupps, B. Fritschel, W. Mavroudakis, M. Mitchell, D. Ridge, J. Wyvratt: Pharm. Technol. 27 (2003) no. 2, 34 – 50.
18. APIC, European Chemical Industries Council: Good Manufacturing Practices in API-Development, Brussels 1999.
[Top of Page]

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page 9 of 9
 Gout Remedies 1

Gout Remedies
Larry J. Silverman, University of Michigan, Ann Arbor, Michigan 48109, United States
Thomas D. Palella, University of Michigan, Ann Arbor, Michigan 48109, United States

1. Introduction . . . . . . . . . . . . . . . 1 3.1.2. Nonsteroidal Anti-inflammatory

2. Gout and Hyperuricemia . . . . . . . 2 Drugs . . . . . . . . . . . . . . . . . . . . 5
2.1. Pathophysiology . . . . . . . . . . . . . 2 3.1.3. Corticosteroids . . . . . . . . . . . . . . 7
3.2. Antihyperuricemic Drugs . . . . . . . 7
2.2. Clinical Manifestations . . . . . . . . 3
3.2.1. Uricosuric Drugs . . . . . . . . . . . . . 7
3. Treatment . . . . . . . . . . . . . . . . . 4 3.2.2. Xanthine Oxidase Inhibitors . . . . . . 8
3.1. Drugs Used to Treat Acute Gout . . 4 3.3. Dietary Management . . . . . . . . . . 9
3.1.1. Colchicine . . . . . . . . . . . . . . . . . 4 4. References . . . . . . . . . . . . . . . . . 9

1. Introduction down of nucleic acids, nucleotides, and ingested,

preformed purines. The proximate steps in uric
Gout is an exclusively human disease. Its car- acid formation are dephosphorylation of ri-
dinal manifestations are high serum urate levels bonucleotides and deoxyribonucleotides to their
(hyperuricemia) and recurrent episodes of acute nucleoside forms, adenosine and guanosine.
arthritis. In its fully developed form, gout also Adenosine and guanosine are both converted to
results in deposition of uric acid in the kidneys inosine. Purine nucleoside phosphorylase con-
(nephrolithiasis), interstitial renal disease, and verts inosine to hypoxanthine in a freely re-
deposition of monosodium urate monohydrate versible reaction. Hypoxanthine, thus generated,
aggregates (tophi) in and around joints (chronic is a substrate for the iron-containing flavoen-
tophaceous gout). zyme, xanthine oxidase. Xanthine oxidase con-
verts hypoxanthine to xanthine, and then xan-
History. The term gout was first introduced thine to uric acid.
in the 13th century, although its clinical mani-
festations had been described by Hippocrates
in the 5th century b.c. [1]. In the 17th century,
Sydenham distinguished gout from other arthri-
tidies [2]. The importance of uric acid in the
pathogenesis of this disease was elucidated in
the 19th century [3].
An understanding of the pathogenesis of gout
has lead to the development of specific thera-
pies. Although colchicine has been used for cen-
turies to treat acute gouty arthritis, newer anti-
inflammatory agents are now used to manage
acute attacks [4]. In addition, effective antihy-
peruricemic therapy has been developed. These
agents decrease serum urate, reduce the total Thus, the production of uric acid is dependent
body pool of uric acid, prevent urate deposition, upon the rate of purine nucleotide degradation
and promote dissolution of preformed tophi and and the subsequent oxidation of hypoxanthine.
stones. The serum concentration of uric acid reflects the
difference between this production rate and the
Biochemistry. Uric acid is the ultimate net excretion rate of uric acid. Under normal con-
degradative product of purine metabolism in hu- ditions, two-thirds of the daily production of uric
mans. It is derived primarily from the break-

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a12 535
2 Gout Remedies
acid is excreted in the urine. The remaining frac-
tion is excreted through the intestine where uric
acid is cleaved by the action of bacterial uricases.
Epidemiology. Hyperuricemia denotes an
elevation of serum urate concentration and may
be defined on either a physicochemical or an
epidemiologic basis. Physicochemically, serum
is saturated with urate at concentrations exceed-
ing 7 mg/dL as measured by the uricase method
at 37 ◦ C [4]. In sex- and age-matched popu-
lations, relative hyperuricemia is present when
the serum urate concentration exceeds two stan-
dard deviations above the mean. In postpuber-
tal men, this value is 7 mg/dL; in postpubertal
females, 6 mg/dL [4]. Epidemiologically, an in-
creased risk for development of gout and kidney
stones exists when the serum urate concentration
exceeds 7 mg/dL [4]. In the majority of subjects,
however, hyperuricemia is asymptomatic. Only
a small fraction of hyperuricemic individuals de-
velop gout [5].
The serum urate concentration varies with
age and sex [6–8]. Values range from 3 to
4 mg/dL in children. With the onset of pu-
berty, serum urate concentration normally rises
in males to 4 – 6 mg/dL and remains at that level
throughout life. In females, the serum urate con-
centration typically remains unchanged until the
menopause at which time it approaches val-
ues comparable to those in adult males. Factors
such as blood pressure, serum creatinine, height,
weight, age, and alcohol intake correlate with
serum urate concentration [9–12].
Serum urate levels above 7 mg/dL are found
in 6.5 – 9.3 % of adult males [4]. Among women,
6.3 % have serum urate values >6 mg/dL [4].
The development of gout depends on the degree
and duration of serum urate elevation. Therefore,
the prevalence of gout increases with age and
with the degree of hyperuricemia [11, 12]. The
annual incidence of gout is 0.1 % for urate lev-
els less than 7 mg/dL and 4.9 % for levels greater
than 9 mg/dL [13].
Symptoms and Treatment. Gout is man-
ifested clinically by recurrent episodes of
acute arthritis. Intraleukocytic crystals of
monosodium urate monohydrate are found in
synovial fluid from inflamed joints [14].
An acute attack of gout is generally self-
limited and confined to a single joint (monoar-
ticular). Recurrent episodes follow, which tend
to become polyarticular. The frequency of at-
tacks increases with time and leads to disabling
chronic arthritis. Prompt diagnosis and imple-
mentation of therapy at the onset of an acute at-
tack shorten the episode and relieve the disabling
pain. Prophylactic therapy aimed at preventing
recurrent arthritis significantly reduces the risk
of chronic arthritis and joint deformity [15]. An-
tihyperuricemic agents lower the serum urate
concentration and thus promote solubilization of
tophi. Reduction of serum urate levels also de-
creases the risks of recurrent arthritis, uric acid
nephrolithiasis, and urate nephropathy, as well
as the development of chronic gouty arthritis.
2. Gout and Hyperuricemia
2.1. Pathophysiology
Hyperuricemia may result from insufficient ex-
cretion of uric acid by the kidneys, endogenous
overproduction of uric acid, or a combination of
both. Primary hyperuricemia develops indepen-
dently of other diseases and is unrelated to drug
use. Secondary hyperuricemia is either a man-
ifestation of an underlying disease or the result
of an ingested drug or toxin.
Impaired Renal Uric Acid Excretion. The
most common cause of hyperuricemia is dimin-
ished uric acid excretion by the kidneys. Al-
though this accounts for approximately 90 % of
cases of primary hyperuricemia [16], the reason
has not been established; impaired urate clear-
ance has been documented in these patients [17–
21].
Underlying renal disease, drugs, or toxins
may also impair the ability of the kidney to ex-
crete uric acid and result in secondary hyper-
uricemia. Intravascular volume contraction re-
sulting from diuretic therapy, adrenal insuffi-
ciency, or liver disease leads to secondary hyper-
uricemia due to diminished glomerular filtration
and increased tubular reabsorption of uric acid
[22, 23]. Drugs such as ethanol, ethambutol, and
nicotinic acid may diminish renal clearance of
uric acid [24]. Organic acids inhibit uric acid
secretion by the kidneys. Therefore, diseases re-
sulting in metabolic acidosis may also lead to
hyperuricemia [24].

Overproduction of Uric Acid. Endogenous
overproduction of uric acid accounts for ap-
proximately 10 % of cases of primary hyper-
uricemia [16]. Overproduction is characterized
by a high level of uric acid in the urine (hy-
peruricaciduria), which is the result of accel-
erated purine synthesis. The etiology of urate
overproduction in primary hyperuricemia is un-
known in the majority of cases, but it may be
due to specific inborn errors of metabolism. Pa-
tients with 5-phosphoribosyl-1-pyrophosphate
synthetase overactivity or partial hypoxanthine
phosphoribosyltransferase (HPRT) deficiency
demonstrate primary hyperuricemia [4].
Endogenous urate overproduction caused by
the following factors may also lead to secondary
hyperuricemia:
1) Inborn enzyme defects resulting in over-
production of uric acid, e.g., the Lesch –
Nyhan syndrome, glucose 6-phosphatase de-
ficiency, and the glycogen storage diseases
types I, III, V, and VII [24]
2) Myeloproliferative disorders leading to ac-
celerated nucleic acid turnover
3) Increased adenosine triphosphate (ATP)
degradation caused by alcohol consumption
or tissue hypoxia [24]
Urate Precipitation. The acute attack
of gout is triggered by precipitation of
monosodium urate monohydrate crystals in or
near a joint [6, 25, 26]. The cause of this pre-
cipitation is unclear, and hyperuricemia is not
essential. The inflammatory response to intra-
articular urate crystals includes activation of
the kallikrein – kinin and complement systems,
formation of leukotrienes, platelet activation,
prostaglandin synthesis [16], and leukocyte mi-
gration. The leukocytes phagocytose the urate
crystals and release chemotactic factors. In-
tracellular urate crystals cause lysosomal dis-
ruption and cell injury. Release of lysosomal
enzymes into the joint space leads to further
inflammatory changes including increased cap-
illary permeability and tissue damage. For a de-
tailed description of inflammation, see → Anti-
inflammatory – Anti-rheumatic Drugs, Chap. 1.
Gout Remedies 3
2.2. Clinical Manifestations
Articular Disease. The clinical spectrum of
gout encompasses four stages:
1) asymptomatic hyperuricemia,
2) acute gouty arthritis,
3) intercritical gout, and
4) chronic tophaceous gout [16].
Asymptomatic hyperuricemia is characterized
solely by elevation of the serum urate concen-
tration. Acute gouty arthritis is usually the first
clinical manifestation of gout and often occurs
after years of asymptomatic hyperuricemia. The
first attack is usually monoarticular and devel-
ops rapidly. The most commonly affected joint
is the metatarsal – phalangeal joint of the big
toe [27], but other joints may be affected [16].
Pain, swelling, and redness develop and inten-
sify within a few hours. Untreated acute gout
is generally self-limited; symptoms persist from
several hours to weeks in severe attacks.
In intercritical gout the first attack of gouty
arthritis is followed by a variable, asymptomatic
period. The majority of patients experience the
second attack within six months to two years,
but the asymptomatic (intercritical) period may
be ten years or longer [16]. During the phase
of intercritical gout, the asymptomatic periods
between acute attacks shorten. The arthritis be-
comes polyarticular, and if untreated, chronic
persistent arthritis may develop [16, 24].
Chronic tophaceous gout is characterized by
chronic polyarticular arthritis and development
of tophi in and around joints and in soft tissues
[16]. Joint erosion and destruction occur, which
may be accompanied by marked deformity and
crippling of hands and feet.
Renal Disease. The clinical manifestations
of hyperuricemia are not limited to articular dis-
ease; three types of renal disease are also found:
(1) uric acid nephropathy, (2) urate nephropathy,
and (3) nephrolithiases.
Uric acid nephropathy results from precip-
itation of uric acid within the collecting ducts
of the kidneys [16]. It is typically associ-
ated with marked hyperuricemia and hyperuri-
caciduria. Uric acid nephropathy is seen most
frequently in lymphoproliferative disorders fol-
lowing chemotherapy [28–30], when the large
4 Gout Remedies
nucleic acid pool liberated by tumor cell lysis
leads to marked hyperuricemia. Acute renal fail-
ure may occur.
Urate nephropathy is caused by deposition
of monosodium urate monohydrate in the renal
interstitium [16]. Unlike uric acid nephropathy,
it does not cause acute renal failure but may con-
tribute to the chronic renal insufficiency of gouty
patients.
Nephrolithiasis. Gouty patients have an in-
creased prevalence of kidney stones [16, 31, 32].
Renal calculi occur in 10 – 25 % of patients with
primary gout and in as many as 42 % of pa-
tients with secondary gout. The incidence of
stone formation increases with increasing serum
urate concentration and urinary uric acid excre-
tion [31, 32].
Other Disorders. Several other disorders are
associated with hyperuricemia and gout; these
include hypertension, obesity, hyperlipidemia,
and diabetes mellitus, as well as cerebrovascular
and cardiovascular disease [16]. No direct cause
and effect relationship has been established bet-
ween these disorders and hyperuricemia.
3. Treatment
Medical management of gout is undertaken to:
1) promote rapid resolution of acute arthritis;
2) reduce the likelihood of recurrent gouty at-
tacks;
3) lower the serum urate concentration, thereby
inhibiting urate deposition and promoting
dissolution of tophi; and
4) prevent uric acid nephrolithiasis.
3.1. Drugs Used to Treat Acute Gout
3.1.1. Colchicine
Colchicine [64-86-8], (S)-N-(5,6,7,9-tetrahy-
dro-1,2-3,10-tetramethoxy-9-oxobenzo[α]hep-
talen-7-yl)acetamide, is an alkaloid of the plant
Colchicum autumnale. The plant has been used
in the treatment of articular disorders since the
sixth century a.d. [33] and colchicine has been
used to treat gout for over two centuries. This
anti-inflammatory drug is uniquely effective
against gouty arthritis (see also → Alkaloids;
→ Anti-inflammatory – Antirheumatic Drugs).
Colchicine impairs leukocyte migration,
thereby inhibiting the inflammation responsi-
ble for acute gouty attacks [34]. Colchicine has
also been shown to inhibit lysosomal degranu-
lation, phagocytosis, and neutrophil adherence
[34–39]. The drug binds to microtubular struc-
tures and arrests cell division [33].
Colchicine is administered orally or intra-
venously [33]. Peak plasma levels occur 0.5 to
2 h after an oral dose. The drug is eliminated
principally through feces; ca. 10 – 20 % is elim-
inated in the urine.
Oral colchicine is used to treat acute gouty
arthritis [16]. The drug is most effective when
administered within the first few hours of an at-
tack at a dose of 0.5 or 0.6 mg/h until symptoms
subside or gastrointestinal side effects develop
(maximum total dosage 6.0 mg). Symptoms usu-
ally improve within 12 h and often completely
resolve within three days. As many as 50 – 80 %
of patients develop gastrointestinal side effects
before relief from arthritis occurs. Daily oral
colchicine (0.5 – 1.0 mg) is useful in preventing
recurrent episodes of acute gout [16].
Intravenous colchicine effectively terminates
acute attacks of gout without causing gastroin-
testinal side effects [16]. It is administered in-
travenously as a single 2-mg dose in 20 mL of
saline, followed by 1-mg dosages every 6 h up to
a maximum of 4 – 5 mg. Complications include
local extravasation with inflammation and skin
necrosis, as well as bone marrow suppression.
3.1.2. Nonsteroidal Anti-inflammatory
Drugs
Several nonsteroidal anti-inflammatory drugs
have been employed in the treatment of acute
gout. These drugs are thought to exert their
anti-inflammatory effects by inhibiting prosta-
glandin synthesis, inhibiting leukotriene syn-

thesis, and preventing free-radical formation
[40]. Prostaglandins are potent mediators of in-
flammation. The nonsteroidal anti-inflammatory
agents reversibly inhibit cyclooxygenase, an en-
zyme that converts arachidonic acid to prosta-
glandin precursors [40]. Prostaglandin synthe-
sis is thereby suppressed. Leukotrienes, also
derived from arachidonic acid, have been im-
plicated in leukocyte aggregation, degranula-
tion, and free-radical formation [40]. Some
nonsteroidal anti-inflammatory agents inhibit
leukotriene synthesis and presumably modify
the inflammatory response by interfering with
these mechanisms.
Oxygen free radicals are formed during the
synthesis of prostaglandins and can cause tissue
injury. Inhibition of prostaglandin synthesis by
nonsteroidal agents suppresses free-radical for-
mation [40].
(For physical properties, syntheses, and trade
names of the drugs treated in this section see
→ Anti-inflammatory – Antirheumatic Drugs).
Indomethacin [53-86-1], 1-(4-chloroben-
zoyl)-5-methoxy-2-methyl-1H-indole-3-acetic
acid (Indocin) is rapidly absorbed from the
gastrointestinal tract. Peak plasma levels are
obtained within 3 h of ingestion [33], and the
drug is highly bound to plasma proteins. It is
eliminated in both urine and feces, 10 – 20 %
being excreted unchanged in the urine. Ap-
proximately 50 % of a given dose undergoes
O-demethylation, and 10 % is conjugated with
glucuronic acid.
For treatment of acute gout, indomethacin is
administered at a 50 – 75-mg dosage, followed
by 50 mg every 6 h for a maximum dose of
200 mg in the first 24 h [16]. The dosage is sub-
sequently reduced [16].
Indomethacin may also be used for gout pro-
phylaxis [16]. A daily dose of 25 – 50 mg is usu-
ally sufficient to prevent recurrence of acute at-
tacks.
Gout Remedies 5
Phenylbutazone [50-33-9], 4-butyl-1,2-di-
phenyl-3,5-pyrazolidinedione (Butazolidin) has
been used for over 30 years to treat acute gout
[41, 42]. After oral administration, peak plasma
concentration is reached within 2 h [33]. The
drug is completely absorbed from the gastroin-
testinal tract and 98 % is bound to plasma pro-
teins. Plasma half-life ranges from 50 to 100 h.
The drug undergoes glucuronidation and hy-
droxylation, and is excreted primarily in the
urine. Oxyphenylbutazone, an active metabolite
of phenylbutazone, has a long plasma half-life
and contributes to the side effects of phenylbu-
tazone. Oxyphenylbutazone is also excreted in
the urine after glucuronidation [33].
For treatment of acute gout, phenylbutazone
is administered at an initial dosage of 200 mg –
600 mg [16], followed by 100 – 200 mg every 6 –
8 h for 24 h (maximum dose = 600 mg/d). The
dosage is then reduced and discontinued after
two days.
Side effects of phenylbutazone include hy-
persensitivity reactions, gastric discomfort, pep-
tic ulcer disease, and fluid retention [33]. Deaths
from aplastic anemia have been reported [43].
Naproxen [22204-53-1], (S)-6-methoxy-α-
methyl-2-naphthaleneacetic acid (Naprosyn)
was effective in acute gout management in sev-
eral clinical trials [44]. It is fully absorbed after
oral administration [33]. Plasma half-life is 12 –
15 h. The drug is extensively bound to plasma
protein and eliminated in the urine. Approxi-
mately 30 % undergoes 6-demethylation prior
to elimination. To treat acute gout, naproxen is
administered at an initial dose of 500 – 750 mg,
followed by 250 mg every 8 h until the acute at-
tack subsides [16].
6 Gout Remedies

Ibuprofen [15687-27-1], α-methyl-4-(2- urine, the major product being the conjugated
methylpropyl)benzeneacetic acid (Motrin) is sulfone. Sulindac administered at a dosage of
absorbed efficiently from the gastrointestinal 200 mg twice a day is effective in terminating
tract [33]. Maximum plasma levels are achieved an acute attack of gout [47].
within 1 – 2 h, and its half-life is approximately
2 h. Like naproxen, ibuprofen is almost com-
pletely bound to plasma proteins and is elimi-
nated principally via the urine. It is metabolized
prior to elimination in the urine. Ibuprofen has
demonstrated efficacy in the treatment of acute
gout [45]. A dosage of 800 mg every 8 h is given
until symptoms are resolved [16]. The dose may
then be reduced.

Piroxicam [36322-90-4], 4-hydroxy-2-

Fenoprofen [31879-05-7], (±)-α-methyl-3-
phenoxybenzeneacetic acid (Nalfon) is rapidly
absorbed, and peak plasma concentrations are
achieved within 2 h of oral administration
[33], [46, pp. 890 – 891]. The plasma half-life
is approximately 3 h. Fenoprofen is highly
bound to plasma protein, and its major urinary
metabolites are fenoprofen glucuronide and 4 -
hydroxyfenoprofen glucuronide. Over 90 % of
the drug is metabolized prior to elimination in
the urine. Successful termination of an acute
gout attack may be achieved with a dosage of
800 mg every 6 h [16]. The dose is then tapered
when symptomatic improvement occurs.
methyl-N-2-pyridyl-2H-1,2-benzothiazine-3-
carboxamide-1,1-dioxide (Feldene) is well
absorbed after oral administration, and peak
plasma concentrations are achieved within 3 –
5 h [46, pp. 1558 – 1559]. Mean plasma half-life
is 50 h. The drug is excreted in both urine and
feces, the majority being excreted as metabo-
lites formed by hydroxylation and conjugation,
cyclodehydration, and hydrolysis of the amide
linkage, decarboxylation, ring contraction, or
N-demethylation. Piroxicam administered at a
daily dose of 20 mg, effectively suppresses or
completely relieves symptoms of acute gouty
arthritis within five days [48–50].

Sulindac [38194-50-2], (Z)-5-fluoro-2-

methyl-1-{[4-(methylsulfinyl)phenyl]meth-
ylene}-1H-indene-3-acetic acid, (Clinoril) is
approximately 90 % absorbed after oral admin-
3.1.3. Corticosteroids
istration [33]. The active sulfide metabolite is
formed by oxidation to the sulfone and subse-
Corticosteroids have both anti-inflammatory
quent reduction. Sulindac has a plasma half-life
and immunomodulatory properties [16]. They
of 7 h; the sulfide metabolite has a half-life of
inhibit arachidonic acid release from phospho-
18 h. Sulindac and its metabolites are exten-
lipids, thereby inhibiting prostaglandin synthe-
sively protein bound. Excretion of the drug oc-
sis. They are also purported to stabilize lyso-
curs in the urine and feces. Approximately 50 %
somal membranes, inhibit cellular metabolism,
of the administered dose is eliminated in the

decrease serum immunoglobulins, and dimin-
ish synovial permeability. Intra-articular cor-
ticosteroids are particularly effective in sup-
pressing acute gouty arthritis [51]. Commonly
used intra-articular steroids include methylpred-
nosolone acetate (Depo-medrol), triamcinolone
acetonide (Kenalog), and triamcinolone hexace-
tonide (Aristopan). Relief of symptoms usually
occurs within 12 h. This form of treatment may
be employed when one or two joints are involved
and the patient is unable to tolerate other forms
of therapy. Many different corticosteroid prepa-
rations are available. For structure, properties,
and preparation, see → Hormones.
3.2. Antihyperuricemic Drugs
The antihyperuricemic drugs consist of (1)
uriscosuric drugs which increase urinary uric
acid excretion and (2) xanthine oxidase in-
hibitors which inhibit uric acid synthesis. The
aim of antihyperuricemic therapy is to lower the
concentration of serum urate below 6.4 mg/dL
[16].
The selection of an antihyperuricemic agent
should be based on the cause of the hyper-
uricemia and the condition of the patient. Pa-
tients without kidney problems who excrete less
than 700 mg of uric acid per day may be treated
with either uricosuric agents or xanthine oxidase
inhibitors [24]. Patients who excrete more than
700 mg of uric acid a day should be treated with
xanthine oxidase inhibitors. Antihyperuricemic
agents should not be given until an acute gouty
attack has subsided because they may exacer-
bate such attacks [16]. In addition, they may also
precipitate the onset of acute gouty arthritis. Pa-
tients should, therefore, be treated prophylacti-
cally with colchicine or indomethacin prior to
the introduction of antihyperuricemic medica-
tion.
3.2.1. Uricosuric Drugs
Uricosuric drugs increase the rate of excretion of
uric acid by interfering with its reabsorption by
the renal tubules [52]. They reduce serum urate
levels in the majority of patients but are gen-
erally ineffective in patients with marked renal
Gout Remedies 7
insufficiency [16]. Concomitant administration
of salicylate blocks their uricosuric effect [52].
The use of uricosuric drugs should be accom-
panied by liberal intake of fluids to prevent crys-
tallization of uric acid within the urinary tract.
Alkalinization of urine by the administration of
sodium hydrogen carbonate or potassium citrate
may prevent formation of kidney stones [24].
Probenecid [57-66-9], 4-[(dipropylamino)-
sulfonyl]benzoic acid (Benemid) inhibits ep-
ithelial transport of organic acids [52]. It is
completely absorbed after oral administration,
with peak plasma levels achieved in 2 – 4 h.
It is extensively bound by plasma proteins
and has a plasma half-life of approximately
9 h. Probenecid is eliminated in the urine.
Metabolism may occur by hydroxylation or con-
jugation to glucuronide [52].
Probenecid is administered at a dose of
250 mg twice a day for one week; the dosage
is then increased up to a maximum of 2 g per
day [46, pp. 1246 – 1247].
Adverse side effects to probenecid include
gastrointestinal irritation, hypersensitivity reac-
tions, and central nervous system abnormalities
[52].
Sulfinpyrazone [57-96-5], 1,2-diphenyl-4-
[2-(phenylsulfinyl)ethyl]-3,5-pyrazolidinedione
(Anturane) is a strong organic acid [52]. Al-
though sulfinpyrazone inhibits reabsorption of
uric acid, like probenecid it interferes with tubu-
lar secretion of other organic acids. It is absorbed
efficiently from the gastrointestinal tract and is
extensively bound to plasma proteins. This drug
is excreted in the urine, with 10 % being the
N1-p-hydroxyphenyl metabolite.
8 Gout Remedies
Sulfinpyrazone is administered initially at a
dose of 50 – 100 mg twice a day, which can be
increased gradually to a daily dosage of up to
800 mg [46, pp. 833 – 834].
Side effects include gastrointestinal irri-
tation, hypersensitivity reactions, and blood
dyscrasias [52]. In addition, this drug may po-
tentiate the action of certain sulfonamides such
as sulfadiazine and sulfisoxazole [46, pp. 833 –
834].
Benzbromarone [3562-84-3], (3,5-dibro-
mo-4-hydroxyphenyl)(2-ethyl-3-benzofura-
nyl)methanone, is a potent uricosuric agent with
demonstrated efficacy in reducing serum urate
levels [53–55]. Onset of uricosuric activity is
rapid, with peak uric acid excretion occurring
at approximately 5 h Benzbromarone does not
affect tubular secretion of other organic acids.
The usual maintenance dose is between 50 and
100 mg a day [53–56]. Side effects include di-
arrhea, allergy, and urolithiasis [53, 54, 56].
Benziodarone [68-90-6] (2-ethyl-3-ben-
zofuranyl)(4-hydroxy-3,5-diiodophenyl)meth-
anone, and zoxazolamine [61-80-3], 5-chloro-
benzoxazolamine, have uricosuric activity [57,
58], but neither agent is used clinically in the
United States to manage hyperuricemia.
3.2.2. Xanthine Oxidase Inhibitors
Xanthine oxidase catalyzes the oxidation of
hypoxanthine to xanthine and of xanthine to uric
acid [24]. Allopurinol and its oxidation prod-
uct oxipurinol are structural analogues of hypo-
xanthine and xanthine, respectively. Both inhibit
xanthine oxidase, thereby diminishing uric acid
synthesis and lowering serum urate concentra-
tion.
Allopurinol [315-30-0], 1,5-dihydro-H-
pyrazolo[3,4-d ]pyrimidin-4-one (Zyloprim) is
absorbed rapidly from the gastrointestinal tract
[33]. Peak plasma levels occur within 30 –
60 min of an oral dose, and plasma half-life is
2 –3 h. Allopurinol is metabolized to oxipurinol
[2465-59-0]. Oxipurinol, 1H-pyrazolo[3,4-d]-
pyrimidine-4,6(5H,7H)-dione is cleared slowly
from plasma and has a half-life of 15 – 20 h [46,
pp. 818 – 820]. Both compounds are biologi-
cally active and neither is protein-bound [33].
Only 10 % of a single dose of allopurinol is
excreted unchanged in the urine.
The usual dosage of allopurinol is 300 mg ad-
ministered once a day. The serum urate concen-
tration falls within the first two days of ther-
apy, and the minimum serum urate construction
is achieved within two weeks [24]. The dose
of allopurinol may gradually be increased to a
maximum of 800 mg daily [46, pp. 818 – 820].
Dosages above 300 mg should be given twice
daily. In patients with renal insufficiency, the
half-life of oxipurinol is increased and the dose
of allopurinol should be reduced.
Side effects of allopurinol therapy include
acute gouty arthritis, hematologic abnormali-
ties, gastrointestinal intolerance [33], and life-
threatening hypersensitivity reactions.
Allopurinol may interfere with the hepatic
metabolism of oral anticoagulant drugs and must
be used with caution in this context [33]. Aza-
thioprine and 6-mercaptopurine are potentiated
when administered concomitantly with allopuri-
nol. The combined administration of allopurinol
and uricosuric drugs may improve serum uric
acid control [33].

3.3. Dietary Management
The aims of dietary management in gout are to
reduce body weight, alcohol intake, and inges-
tion of foods known to trigger acute attacks [16].
Patients with gout are often overweight [16];
weight reduction may lower the serum urate con-
centration [59].
Alcohol intake may lead to hyperuricemia
and gout [60], therefore patients with gout
should reduce or discontinue alcohol consump-
tion.
Ingestion of certain, often purine-rich, foods
may be associated with the development of
acute gouty arthritis in some patients [16]. Spe-
cific foods known to precipitate acute attacks
of gout should be avoided. Examples of purine-
rich foods are herrings, sardines, liver, sweet-
breads, kidneys, and brewer’s yeast. Severe di-
etary restriction of purine is usually unnecessary,
but patients should avoid excessive purine in-
take. High-protein diets should also be avoided
because endogenous purine production is in-
creased by excessive protein consumption [16].
Obesity, hyperlipidemia, and hypertension
are associated with gout and hyperuricemia [16].
Management of these conditions with diet, ex-
ercise and appropriate medications is important
in prolonging life and preventing the complica-
tions of these associated conditions.
This work is supported by National Institutes
of Health Grant Number DK-19045. Dr. Palella
is the recipient of an Arthritis Investigator Award
from the Arthritis Foundation.
4. References
1. Hippocrates: The Genuine Works of
Hippocrates, vols. 1 and 2, translated from
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2. T. Sydenham: Tractatus de Podagra et
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3. A. B. Garrod, Trans. M-Chir. Soc. Edinburgh
31 (1848) 83 – 97.
4. J. B. Wyngaarden, W. N. Kelley: Gout and
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5. H. E. Paulus, A. Coutts, J. J. Calabro, J. R.
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Gout Remedies 9
6. W. M. Mikkelsen, H. J. Dodge, H. Valkenburg,
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7. S. Akizuki, Ann. Rheum. Dis. 41 (1982)
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8. W. R. Harlan, J. Cornoni-Huntley, P. E.
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10. D. Kuntz, J. M. Chretien, A. Ryckewart, Sem.
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11. J. Zalokar, J. Lellouch, J. R. Claude, Sem. Hop.
(Paris) 57 (1981) 664 – 670.
12. K. Nishioka, K. Mikanagi, Adv. Exp. Med.
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14. D. J. McCarty, J. L. Hollander, Ann. Intern.
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15. T-F. Yu, A. B. Gutman, Ann. Intern. Med. 55
(1961) 179 – 192.
16. W. N. Kelly, I. H. Fox in W. N. Kelley, E. D.
Harris, S. Ruddy, C. B. Sledge (eds.): Textbook
of Rheumatology, 2nd ed., W. B. Saunders
Co., Philadelphia 1985, pp. 1359 – 1398.
17. C. A. Nugent, W. D. MacDiarmid, F. H. Tyler,
Arch. Intern. Med. 113 (1964) 115 – 121.
18. J. T. Scott, M. L. Snaith, Ann. Rheum. Dis. 30
(1971) 285 – 289.
19. J. B. Haupt, M. A. Ogryzla, Arthritis Rheum. 7
(1964) 316.
20. J. E. Seegmiller, A. I. Grayzel, R. R. Howell, C.
Plato, J. Clin. Invest. 41 (1962) 1094 – 1098.
21. W. Latham, G. P. Rodman, J. Clin. Invest. 41
(1962) 1955 – 1963.
22. I. H. Fox in J. A. Spittell (ed.): Clinical
Medicine, Harper & Row, Philadelphia 1982.
23. E. I. Feinstein, V. H. Quion, E. M. Kaptein,
S. G. Massry, Am. J. Nephrol. 4 (1984) 77.
24. T. D. Palella, I. H. Fox in C. R. Scriver, A. L.
Beaudet, W. S. Sly, D. Valle (eds.): Methabolic
Basis of Inherited Disease, 6th ed.,
McGraw-Hill, New York 1988, in press.
25. N. J. Zvaifler, T. J. Pekin, Arch. Intern. Med.
111 (1963) 99 – 102.
26. J. E. Seegmiller, L. Laster, R. R. Howell, N.
Engl. J. Med. 268 (1963) 712 – 716.
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27. C. Scudamore: A Treatise on the Nature and
Cure of Gout and Rheumatism, including
General Consideration on Morbid States of the
Digestive Organs: Some Remarks on Regimen
and Practical Observations on Gravel, 2nd
ed., Longman, London 1817.
28. E. Frei, C. J. Bentzel, R. R. Rieselbach, J. B.
Block, J. Chronic Dis. 16 (1963) 757 – 776.
29. R. E. Rieselbach et al., Am. J. Med. 37 (1964)
872 – 884.
30. C. M. Kjellstrand, D. C. Campbell, B. von
Hartitzsch, T. J. Buselmeier, Arch. Intern. Med.
133 (1974) 349 – 359.
31. A. B. Gutman, T.-F. Yu, Am. J. Med. 45
(1968) 757 – 779.
32. T-F. Yu, A. B. Gutman, Ann. Intern. Med. 67
(1967) 1133 – 1148.
33. R. J. Flower, S. Moncada, J. R. Vane in A. G.
Gilman L. S. Goodman, A. Gilman (eds.): The
Pharmacological Basis of Therapeutics, 6th
ed., Macmillan Publ. Co., New York 1980,
pp. 682 – 728.
34. S. E. Malawista, Arthritis Rheum. 18 (1975)
835 – 846.
35. R. B. Zurier, S. Holfstein, G. Heissman, J. Cell
Biol. 58 (1973) 27 – 41.
36. Y. H. Cheng, Arthritis Rheum. 11 (1968) 473.
37. R. I. Lehrer, J. Infect. Dis. 127 (1973) 40 – 48.
38. R. Penney, D. A. G. Galton, J. T. Scott, V.
Eifen, Br. J. Haematol. 12 (1966) 623 – 632.
39. E. Dellaverde. P. T. Fan, Y. H. Chang, J.
Pharmacol. Exp. Ther. 223 (1982) 197 – 202.
40. H. E. Paulus, D. E. Furst in D. J. McCarty
(ed.): Arthritis and Allied Conditions, 10th
ed., Lea & Febiger, Philadelphia 1985,
pp. 453 – 486.
41. R. H. Freyberg, Arthritis Rheum. 5 (1962)
624 – 632.
42. A. B. Gutman, Arthritis Rheum. 8 (1965)
911 – 920.
43. M. F. Cuthbert, Curr. Med. Res. Opin. 2
(1974) 600 – 610.
Graphite → Carbon
44. R. F. Willkins, J. B. Case, F. J. Huix, J. Clin.
Pharmacol. 15 (1975) 363 – 366. R. A. Sturge
et al., Adv. Exp. Med. Biol. 76 B (1977)
290 – 296.
45. M. C. Schweitz, D. J. Nashel, F. P. Alepa, J.
Am. Med. Assoc. 239 (1978) 34 – 35.
46. E. R. Barnhart (ed.): Physicians Desk
Reference, 41st ed., Medical Economics Co.,
Oradell, N.J., 1987, pp. 890 – 891.
47. G. N. Karachalios, G. Donas, Int. J. Tissue
React. 4 (1982) 297 – 299.
48. E. Murpy, J. Int. Med. Res. 7 (1979) 507 – 510.
49. G. N. Karachalios, Clin. Exp. Rheum. 3 (1985)
63 – 65.
50. R. H. Bluestone, Am. J. Med. 72 (1982)
66 – 70.
51. J. L. Hollander, J. Bone, Joint Surg. 35 A
(1953) 983 – 990.
52. G. H. Mudge in A. G. Gilman, L. S. Goodman,
A. Gilman (eds.): The Pharmacological Basis
of Therapeutics, 6th ed., Macmillan Publ. Co.,
New York 1980, pp. 929 – 934.
53. A. Masbernard, C. P. Giudicelli, S. Afr. Med. J.
59 (1981) 701 – 706.
54. W. A. M. Scott, J. Int. Med. Res. 9 (1981)
82 – 87.
55. G. W. Schepers, J. Int. Med. Res. 9 (1981)
511 – 515.
56. R. Bluestone, J. Klinenberg, I. K. Lee, Adv.
Exp. Med. Biol. 122 A (1980) 283 – 286.
57. G. Lemieux, P. Vinay, A. Gougoux, G.
Michaud, Am. J. Phys. 224 (1973)
1440 – 1449.
58. J. J. Burns, T.-F. Yu, L. Berger, A. B. Gutman,
Am. J. Med. 25 (1958) 401 – 408.
59. B. T. Emmerson, Aust. N. Z. J. Med. 3 (1973)
410.
60. J. Faller, I. H. Fox, N. Engl. J. Med. 307
(1982) 1598 – 602.
 Gravity Concentration 1

Gravity Concentration
See also → Solid – Solid Separation, Introduction
Richard O. Burt, Tantalum Mining Corporation of Canada Ltd., Lac du Bonnet, Manitoba, Canada REO
1 AO

1. Introduction . . . . . . . . . . . . . . . . . 1 6. Shaking Separators . . . . . . . . . . . . 6

2. Principles . . . . . . . . . . . . . . . . . . . 1 7. Slime Separators . . . . . . . . . . . . . . 7
3. Choice of Equipment . . . . . . . . . . . 2 8. Dry Gravity Concentration . . . . . . . 8
4. Stratification Devices . . . . . . . . . . . 4 9. Flow Sheet Example . . . . . . . . . . . . 8
5. Flowing-Film Devices . . . . . . . . . . . 5 10. References . . . . . . . . . . . . . . . . . . 8

1. Introduction
Gravity concentration is the separation of one or
more minerals, usually of different density, from
others by relative movement in response to the
force of gravity and other forces.
Next to handpicking, gravity concentration
is the most ancient mineral-processing method,
with early practices described over 2000 years
ago [1]. One of the classic works on the subject
is the 6th century book by Agricola [2]. In the
20th century, the importance of gravity concen-
tration declined somewhat as other processes,
such as flotation or magnetic and electric sep-
aration methods, were developed (→ Flotation,
→ Magnetic Separation, → Electrostatic Sepa-
ration). Nevertheless, it remains one of the ma-
jor recovery processes in both mineral process-
ing and, especially, coal preparation (→ Coal,
Chap. 7.1.2.1.). Furthermore, the development
of high-capacity equipment, along with height-
ened awareness of the negative environmental
impact of many chemicals used in flotation and
leaching, has resulted in renewed interest in
gravity concentration for a wide range of prod-
ucts.
Today gravity concentration is used for a di-
verse range of minerals: from andalusite to zir-
con, from coal to diamond, from mineral sands
to metal oxides, and from industrial minerals to
gold.
2. Principles
Important factors in determining the relative
movement of a particle in a fluid include relative
density, mass, size, and shape of the particle.
If, in a hypothetical two-mineral separation,
only one of these factors is significantly differ-
ent, separation is relatively easy. In nearly every
case, however, the variety of minerals present
have different relative densities and a range of
particle masses, sizes, and shapes. The ease or
difficulty of separating one species from an-
other depends on the relative differences bet-
ween these factors and whether such differences
assist or oppose separation. Some idea of the
ease of separating two minerals can be obtained
from the concentration criterion (CC), which is
defined as follows:
dh −df
CC =
dl −df
where d h is the relative density of the heavy min-
eral; d l the relative density of the light mineral;
and d f the density of the suspending fluid.
In general, if CC > 2.5, then separation is rel-
atively easy; however, if CC < 1.25 separation
is not likely to be effective. For developmental
test work, the concentration criterion is not suf-
ficiently accurate, and tests involving heavy-liq-
uid separation should be carried out (→ Dense-
Medium Separation, Chap. 5.).
Gravity concentration is effected by the rela-
tive movement of minerals of different density in
response to gravity and one or more other forces,
which often include the resistance to motion of-
fered by a viscous fluid. One characteristic of
all separation devices is that, for the particles to

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.b02 21
2 Gravity Concentration
move relative to one another, at some stage of
the process the particles must be kept slightly
apart, or dilated, by the superimposed force.
No single mechanism can satisfactorily ex-
plain the behavior of any particular device; a
combination of two or more mechanisms comes
closer to describing the operation (but rarely
does so completely). Conversely, however, var-
ious mechanisms have been proposed that are
common to apparently diverse items of equip-
ment and gravity concentration processes, and
these are a useful means of classifying the vari-
ous devices (see Fig. 1) [3].
Figure 1. Mechanisms in gravity concentration
A) Density; B) Stratification; C) Flowing film; D) Shaking
◦ = light; • = heavy
Density (Fig. 1 A). The viscous fluid used
has a density, or apparent density, between that
of the minerals to be separated. Thus, one min-
eral(s) has a net positive buoyancy and floats,
whereas the other(s) has a net negative buoyancy
and sinks. This classification includes dense-
medium separation (→ Dense-Medium Separa-
tion), one of the most important gravity concen-
tration processes, and magnetohydrostatic sepa-
ration.
Stratification (Fig. 1 B). An intermittent flu-
idization caused by the pulsation of the fluid in a
vertical plane stratifies the various mineral con-
stituents. This classification applies to a wide
range of jigs.
Flowing Film (Fig. 1 C). The constituents
are separated by their relative movement through
a stream of slurry, which flows down a plane by
the action of gravity. Flowing-film concentra-
tion is the oldest process used in gravity concen-
tration and remains of major importance, with
such units as the sluice, pinched sluice, Reichert
cone, and, through inclusion of lateral move-
ment caused by the addition of centrifugal force,
the spiral.
Shaking (Fig. 1 D). The mineral components
are stratified by superimposing a horizontal
shear force on the flowing film. This force can
be oscillating, as in a shaking table, or orbital,
as in the Bartles – Mozley separator or crossbelt
concentrator.
The theoretical aspects of these and other
mechanisms involved in gravity separation are
discussed in [4].
3. Choice of Equipment
A wide range of gravity concentration equip-
ment is available. Factors that determine choice
of the correct unit include the size range of the
particles to be separated, the duty required, the
desired throughput and efficiency, and–all other
things being equal–the unit cost, both capital and
operating, of the equipment.
Size Range. The overall particle-size range
that can be separated by using gravity concen-
tration is larger than for any other process. Par-
ticles can be separated from each other as long
as there is a suitable density differential between
them; however, the top size may be limited by
the mechanical handling ability of the device,
500 mm is generally accepted as the largest size
for separation. The practical lower cutoff limit
for fine gravity concentration is ca. 6 µm.
No device is capable of treating the entire size
range amenable to gravity concentration. In ad-
dition, few devices operating as a single unit can
efficiently treat the complete range which they
are designed to handle. Therefore, some form
of feed preparation is normally required. Fig-
ure 2 indicates the optimum size range for some
of the more common equipment types [4]. Jigs,
Reichert cones, and sluices are essentially mass
classification devices and are capable of treat-
ing a fairly wide range of sizes, but some loss of
efficiency occurs at the top, bottom, and middle
of the size range. Treatment of material in series
circuits is practical with these units (Fig. 3).
 Gravity Concentration 3

Other types of equipment (e.g., the table or

Bartles – Mozley separator, concentrating by re-
verse classification, or the spiral concentrating
by hindered settling) operate significantly bet-
ter on sized or classified feed, and treatment in
parallel circuits is required (Fig. 4).
Generally, the two types of circuit are com-
bined. For example, a series circuit of jigs treat-
ing unsized feed may be followed by a sizing
step, sized fractions being heated on a parallel
circuit of tables and film sizing units.

Capacity. The capacity range of gravity con-

Figure 2. Operating range of gravity concentration equip-
ment
A) Stratification devices: a) jig
B) Flowing-film devices: b) Sluice box; c) Reichert cone;
d) Pinched sluice; e) Spiral
C) Shaking devices: f) Shaking table; g) Bartles – Mozley;
h) Crossbelt
D) Air devices: i) pneumatic jig; j) Air table
E) Miscellaneous devices: k) centrifugal separators
centration equipment is enormous (from a few
kilograms per hour to ca. 1000 t/h per unit).
Whereas sluices and jigs are manufactured in
a variety of sizes suited for a range of capac-
ity, other items are produced in one or two
sizes only, and high throughputs require mul-
tiple units. Typical capacities for gravity con-
centration equipment are as follows (in tons per
hour):

Jig ≤800
Sluice ≤500
Reichert cone 60 – 70
Spiral 1 – 12
Table (ore) 0.2 – 2
Table (coal) 8 – 12
Bartles – Mozley Separator 2 – 2.5
Crossbelt Concentrator 0.3 – 0.5
Centrifugal 1 – 15

Efficiency. Most devices can efficiently sep-

arate materials containing only very heavy and
very light fractions. However, most materials
consist of particles with a range of densities. The
Figure 3. Series circuit more efficient a device, the more capable it is of
a) Jig; b) Screen; c) Jig effectively separating near-density particles [5].
Equipment efficiency classified by this mea-
sure is shown in Table 1.
Table 1. Process applicability–density of separation

Wt % of feed Degree of Type

within ±0.10 kg/L difficulty
of density of expected
separating medium

0–7 simple sluices, jigs

7 – 10 relatively cones
simple
10 – 15 moderately tables
difficult spirals, DMS ∗
>15 difficult DMS ∗
Figure 4. Parallel circuit
a) Hydrosizer; b) Spiral; c) Shaking table; d) Cyclone; ∗ Dense-medium separation
e) Crossbelt concentrator
4 Gravity Concentration
4. Stratification Devices
Jigs sort by movement of a bed of particles,
which are intermittently fluidized by pulsation
of the fluid in a vertical plane. The particles be-
come arranged in layers, with density increas-
ing from top to bottom. This particle arrange-
ment (stratification) results from several contin-
uously varying forces which act on the particles.
Although many types of jigs are manufactured,
their construction principles are similar (Fig. 5).
Figure 5. Basic construction of a jig
a) Jig bed; b) Ragging; c) Jig screen
Figure 6. Three mechanisms of jigging
A) Differential acceleration; B) Hindered settling; C) Inter-
stitial trickling
◦ = light; • = heavy
Theories postulated to describe the action of
the jig include differential acceleration, hindered
settling, and interstitial trickling (Fig. 6). Differ-
ential (initial) acceleration at the start of particle
movement is related to particle density, rather
than particle size or mass. Hindered settling oc-
curs once the particles have reached their termi-
nal velocity; movement is related to mass. In the
interstitial trickling phase, movement is related
to particle size. An alternative theory proposes
that the mechanism of concentration is the at-
tainment of minimum potential energy in the het-
erogeneous mass [6]. Each of these mechanisms
undoubtedly plays some part in the stratification
process; however, which (if any) is the most im-
portant is open to question. Because the design
of the pulsation cycle (i.e., duration of the cycle
and the intensity of both upward and downward
pulsation) can be varied, different manufacturers
have developed units that accentuate different
mechanisms.
Figure 7. Typical jigs
A) Baum and OPM; B) Denver; C) Bendelari; D) IHC
a) Air box; b) Jig bed; c) Screen; d) Diaphragm
Jigs that rely on a long pulsation phase and
a short suction phase, such as the Baum, OPM
(Fig. 7 A), and Batac coal-washing jigs, tend to
have a high capacity at the expense of recovery
of finer particles. Although less efficient than
heavy-medium separation, the high capacity and
low operating cost of these jigs ensure that they
 Gravity Concentration 5

remain the primary means of concentrating ther- depth as the width of the sluice decreases. At
mal coal as well as metallurgical coal where the the end of the channel, the slower moving lower
amount of near-density shale is not excessive. level of the stream, enriched in heavy minerals,
Units with a longer suction phase, such as the is peeled away from the main stream by a splitter
Denver, Bendelari, and IHC (Fig. 7 B – D), ex- (b).
hibit a higher recovery of fines with some com-
promise to capacity. Therefore, these units are
more commonly used for mineral recovery, such
as alluvial tin or hard-rock gold ores.

5. Flowing-Film Devices
When a film of water flows down an inclined sur-
face under laminar conditions, the velocity dis-
tribution is parabolic, being zero at the bottom of
the film and maximal at the top. When mineral
particles of different size and relative density are
introduced into this laminar film, they arrange Figure 9. Pinched sluice
A) Cross section: a) Concentrating segment; b) Splitter
themselves in the general downslope sequence B) Plan view
shown in Figure 8. A variety of devices use this
mechanism for separation.
A variety of pinched sluice designs are used,
especially in Australia. Elsewhere, the more
common variant is the Reichert cone (Fig. 10).
The inverted cone concentrating surface of this
device may be viewed as a number of pinched
sluices placed adjacent to one another to form
a circle, without any sidewalls to interfere with
Figure 8. Particle arrangement on an inclined surface
◦ = light; • = heavy stratification [7]. The cone concentrator consists
of a number of stages in series and in parallel;
it can thus achieve multiple stages of separation
Sluice Box. A sluice box is essentially an in- in one unit. This is important because neither
clined trough or launder, usually of rectangular cone nor sluice is particularly efficient in a sin-
cross section, through which a wide size range gle stage.
of feed is washed by a large volume of water.
A series of riffles is arranged at the bottom of
the sluice box so as to provide some turbulence
between each riffle and allow concentration of
heavies.
These units are relatively inefficient and gen-
erally used only for alluvial mining in areas
where power is not readily available.

Pinched Sluice and Reichert Cone. The

principle of operation of a typical pinched sluice
is shown in Figure 9.
Pulp, at a high solids density, enters the chan-
nel in a relatively thin stream at the upper or
wider end. As this stream flows down the sluice, Figure 10. Reichert cone
a) Feed distributor; b) Double-cone assembly; c) Adjustable
the finer and heavier particles concentrate (a) in insert; d) Single-cone assembly; e) Variable insert
the lower levels of the stream and increase in
6 Gravity Concentration
The advantages of the Reichert cone are its
high capacity, low capital cost per unit through-
put, light weight, compactness, and metallurgi-
cal performance. Cones have two disadvantages:
one is the need for a feed with 60 % solids be-
cause the device is sensitive to variations in pulp
density; the other is that cones are unsuitable for
operations with a new feed rate of less than ca.
50 t/h.
Spiral Concentrator. Spiral concentrators
are used widely in mineral processing and, more
recently, in coal preparation. The basic design of
the spiral has remained virtually unchanged for
many years (Fig. 11).
Figure 11. Spiral concentrator
a) Center column; b) Splitter; c) Wash-water channel;
d) Concentrate pipe
Recently, however, spiral technology has de-
veloped rapidly, more so perhaps than that of
any other gravity concentrator. Developments,
mainly in Australia, the former Soviet Union,
the Peoples Republic of China, and the United
States, have included the introduction of a range
of trough profile, pitch, and diameter; the intro-
duction of limited offtake spirals; and the use of
spirals that do not require wash water [8]. The
correct choice of these parameters for a specific
duty is probably the most important factor in ef-
ficient spiral flow sheet design.
Concentration in a spiral is a complex blend
of a variety of forces: hindered settling clas-
sification, interstitial trickling, Bagnold shear,
and stream cross-sectional rotation. Many grav-
ity concentration devices use the first two forces,
several employ the first three, but the addition of
cross-sectional rotation makes the spiral unique
as a self-compensating device.
6. Shaking Separators
Shaking Table. The shaking table (Fig. 12)
remains one of the workhorses of the mineral-
processing industry [9].
Figure 12. Shaking table
a) Feedbox; b) Wash water; c) Deck; d) Riffles; e) Shaking
mechanism; f) Supports
The forces by which the shaking table sepa-
rates the heavy particles from the lights are com-
plex and, to some extent, opposing. Particles are
stratified into discrete layers behind a series of
riffles (Fig. 13) by superimposing, on the flowing
film, a horizontal, asymmetrically reciprocating
shear force acting laterally to the flow. The strat-
ified layers are separated from each other by a
lateral movement caused by the asymmetry of
the shear force.
Figure 13. Stratification behind riffles
The multidecked Concenco (USA) and SKO
(former states of USSR) units are ideally suited
for roughing duties in larger plants and for coal
preparation; the latter application is by far the
most important in terms of volume. Single-deck
units with mechanical head motions, such as
the Holman (UK), Deister (USA), SKM (for-
mer states of USSR), Wilfley (UK and USA),
and Yun Tin (Peoples Republic of China) types,
are better suited for smaller plants or for clean-
ing duty, mainly in mineral processing. In such
operations, careful feed preparation and treat-
ment of table middlings on separate equipment
are essential for optimum performance.

7. Slime Separators
The inherent difficulty of recovering very fine
particles (< 50 µm) by gravity has led to the de-
velopment and, in many cases, obsolescence of
a more diverse range of equipment than for any
other particle-size range.
The Endless Belt concentrator and Johnson
barrel are used in South Africa to recover fine
gold in milling circuits. Likewise, the Rocking –
Shaking vanner is used in China for the treatment
of tin, tungsten, and iron ores. The more widely
used Bartles – Mozley separator and the Bartles
Crossbelt concentrator superimpose, an orbital
shear motion on a slightly inclined surface, and
are capable of recoveries as fine as 6 µm. The
former (Fig. 14) is a semibatch device that dis-
charges concentrates discontinuously; the latter
is a continuous device that uses a slowly mov-
ing belt to remove concentrates from the pulp
stream.
Figure 14. Bartles – Mozley separator
A) Collecting step: a) Feedwater valve assembly; b) Two
sandwiches; c) Product launders
B) Discharging step: d) Suspension cables; e) Tilt cylinder;
f) Main frame
Spiral sluices are popular in both the for-
mer Soviet Union and the Peoples’ Republic of
China. Similar in principle to the spiral separa-
tor, the cross section of the helix is much flat-
ter, enabling recoveries as fine as 15 µm to be
achieved.
The GEC (General Electric Co.) Duplex con-
centrator uses side shear rather than orbital shear.
It is a semibatch device, with the decks tilting
sideways rather than lengthways as on the Bar-
tles – Mozley separator. Centrifugal separators
are growing in popularity. The Knelson concen-
trator consists of a riffled basket rotating on a
Gravity Concentration 7
vertical axis with a continuous supply of back-
pressure water in the riffles to keep the bed of
ore (usually gold) mobile. The Yunnan separa-
tors used in China for iron, gold, and metal ox-
ide recovery are smooth-walled drums rotating
on a horizontal axis. Both units are semibatch
devices.
8. Dry Gravity Concentration
The majority of commercially available, dry
gravity concentration processes are similar in
principle to their wet gravity concentration
counterparts. The latter include dense media
separation, jigging, pinched sluices, and tabling.
Although the mechanisms of separation of the
wet and dry units may not be the same, the wet
units already described make a reasonable point
of reference for their dry counterparts. Other dry
gravity concentration devices, which do not have
a direct counterpart in wet concentration, have
been developed. These include the fluidized-bed
separator and the zigzag.
All dry concentrating equipment, except the
dry jig, uses a constant controlled upflow of flu-
idizing air. The dry jig, however, uses a pulsating
air flow; pulsation effects stratification in a man-
ner comparable to its counterpart in wet concen-
tration.
Dry separators generally require closely sized
feed and are less efficient than wet separators.
Consequently, they are used only where water is
not available, or for “cleanup” of rough concen-
trates already dried for other processes.
9. Flow Sheet Example
Apart from sample separations, plants rarely in-
corporate only one type of device. This is espe-
cially true of metal oxide plants. Figure 15 (see
next page) is an example of the complex flow
sheet that may be required to maximize both re-
covery and purity of the valuable minerals.
Acknowledgment . Material from this sec-
tion is drawn mainly from the book Gravity Con-
centration Technology, written by the author (as-
sisted by C. Mills) and published by Elsevier
Science Publishers BV, Amsterdam, who retain
the copyright. Their permission to utilize this
material is duly acknowledged.
8 Gravity Concentration

Figure 15. Example of gravity concentration circuit

a) Reichert cone; b) Spiral; c) Grinding mill; d) Cyclone; e) Classifier; f) Shaking table; g) Crossbelt concentrator; h) Bartles –
Mozley separator

10. References 6. F. W. Mayer: Proc. 7th Int. Mineral Processing

1. C. P. S. Pliny: Natural History Book 33, ca. 70
A.D.
2. G. Agricola: De Re Metallica, translated by
H. C. Hoover, L. H. Hoover, Dover
Publications, New York 1950, Book XIII.
3. E. G. Kelly, D. J. Spottiswood: Introduction to
Mineral Processing, Wiley Interscience, 1982.
4. R. O. Burt (assisted by C. Mills): Gravity
Concentration Technology, Elsevier,
Amsterdam 1984.
5. J. W. Leonard, D. R. Mitchell: Coal
Preparation, 3rd ed., AIME, New York 1968,
Section 4, pp. 23 – 30.
Cong., Gordon and Breach, New York 1964,
pp. 75 – 97.
7. J. J. Ferree, Min. Eng. 25 (1973) no. 3, 29 – 31.
8. R. O. Burt, A. V. Yashin, Mineral
Processing & Extract. Metall., IMM. London
1984, pp. 117 – 128.
9. R. O. Burt, XV. Int. Mineral Processing Cong.,
Cannes 1985, pp. 272 – 281.
10. A. V. Yashin, M. F. Anekin, V. A. Skrepko,
Spiral Concentrator Operation, Nedra Press,
Moscow 1984, pp. 54 – 65.

Grignard Reaction → Magnesium Compounds

Grinding → Abrasives
Grinding → Size Reduction
Grouting, Chemical → Cement and Concrete
Grouting, Chemical → Silicates
Guanamines → Melamine and Guanamines

Guanidine and Derivatives
Thomas Güthner, Degussa AG, Trostberg, Germany
Bernd Mertschenk, Degussa AG, Trostberg, Germany
Bernd Schulz, Nigu Chemie GmbH, Waldkraiburg, Germany
1. Guanidine and Guanidine Salts . . .
1.1. Properties . . . . . . . . . . . . . . . . .
1.2. Production . . . . . . . . . . . . . . . .
1.2.1. Guanidine Salts from Dicyandiamide
1.2.2. Guanidine Salts from Cyanamide . . .
1.2.3. Guanidine Salts from Urea . . . . . . .
1.2.4. Other Processes . . . . . . . . . . . . . .
1.3. Environmental Protection . . . . . .
1.4. Quality Specifications . . . . . . . . .
1.5. Analysis . . . . . . . . . . . . . . . . . .
1.6. Storage and Transportation . . . . .
1.7. Legal Aspects . . . . . . . . . . . . . . .
1.8. Uses . . . . . . . . . . . . . . . . . . . . .
1.8.1. Pharmaceuticals . . . . . . . . . . . . . .
1.8.2. Plant Protection . . . . . . . . . . . . . .
1.8.3. Cosmetics . . . . . . . . . . . . . . . . .
Guanidine salts are made from cyanamide or
dicyandiamide by addition of ammonium salts.
The highly soluble guanidine hydrochloride is
mainly used in pharmaceutical and biotech ap-
plications, while guanidine nitrate is used in
propellants and explosives.Nitroguanidine, pre-
pared by nitration of guanidine nitrate, is used
for explosives and as a building block for
neonicotinoid insecticides. Aminoguanidines,
prepared from hydrazines and cyanamide or
guanidines, are mainly used for agrochemi-
cals and — due to their high nitrogen con-
tent — as a component for propellants and gas
generators.Organoguanidines can be prepared
from cyanamides or cyanogen chloride. They
are used as building blocks for agrochemicals
and pharmaceuticals, and as curing agents for
plastics and rubbers. Biguanides can be obtained
from dicyanamide or cyanoguanidines, they are
mainly used as pharmaceuticals and biocides.

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a12 545.pub2
Guanidine and Derivatives 1
1 1.8.4. Textile Impregnation, Flame Retar-
1 dants, Paper and Resin Manufacture . 7
2 1.8.5. Propellants and Explosives . . . . . . . 7
2 1.8.6. Biotechnological Applications of
4 Guanidine Salts . . . . . . . . . . . . . . 7
4 1.9. Economic Aspects . . . . . . . . . . . . 8
5 2. Derivatives . . . . . . . . . . . . . . . . 8
5 2.1. Nitroguanidine . . . . . . . . . . . . . 8
5 2.2. Aminoguanidine . . . . . . . . . . . . 8
6 2.3. Diamino- and Triaminoguanidine . 9
6 2.4. Organoguanidines . . . . . . . . . . . 10
6 2.4.1. Alkylguanidines . . . . . . . . . . . . . 10
6 2.4.2. Arylguanidines . . . . . . . . . . . . . . 11
6 2.5. Biguanide and Derivatives . . . . . . 13
7 3. Toxicology and Occupational Health 14
7 4. References . . . . . . . . . . . . . . . . . 14
1. Guanidine and Guanidine Salts
Guanidine [113-00-8], CH5 N3 , M r 59.08, was
first isolated in 1861 by Strecker as a degrada-
tion product of guanine [73-40-5].
Although free guanidine or guanidine salts
naturally occur only in trace amounts [1], many
guanidine derivatives are important components
of living organisms [2 – 4]. Guanidine and its
derivatives have a wide field of application, e.g.,
as building blocks in the synthesis of pharma-
ceutical and agricultural chemicals, in the manu-
facture of textiles and plastics, and also in bio-
chemistry [5 – 8].
1.1. Properties
Free guanidine can be isolated from guanidine
salts by reaction with a strong base such as an
2 Guanidine and Derivatives

alkali metal hydroxide or methoxide. After re-

moval of the precipitated salt the free guanidine
base is obtained as colorless, waxy, very hygro-
scopic crystals (mp <50 ◦ C).
Guanidine is a strong monobasic Brønsted Nitration of guanidine leads to nitroguani-
base, which absorbs water and carbon dioxide dine (see Chap. 2.1), while chlorination with
from the air and forms strongly alkaline solu- elemental chloride or sodium hypochlorite leads
tions with water and alcohols; the pH of a 20 to N,N  -dichloro-diazenedicarboxamidine
wt % aqueous solution is ca. 13.5 (25 ◦ C). In (azochloramide, [502-98-7]).
aqueous solution at elevated temperature guani-
dine is hydrolyzed to urea; airtight alcohol solu-
tions are stable. Guanidine is infinitely soluble
in water, ethanol, methanol, and dimethylform-
amide.
Protonation of guanidine gives the me-
someric, highly stabilized guanidinium cation:

Guanidine forms stable, easily crystallizable
salts with acids, even with a weak acid such as
stearic, carbonic, or silicic acid. Some physical
properties of various guanidine salts are listed in
Table 1.
Salts of guanidine should, according to IU-
PAC nomenclature, be named as guanidinium
compounds. In this article, however, common
(although technically incorrect) names will be
used, e.g., guanidine nitrate rather than guani-
dinium nitrate.
The very stable guanidinium cation is unreac-
tive, so reactions of guanidine with organic com-
pounds are usually carried out under strongly al-
kaline conditions. Like other amines, guanidine
undergoes alkylation, acylation, methylolation,
and condensation. Many guanidine derivatives
are synthesized from guanylating agents such as
cyanamide [420-04-2] (→ Cyanamides) or O-
methylisourea [2440-60-0] (see Sect. 2.4) be-
cause of the relatively low reactivity of guani-
dine itself.
The most important reaction of guanidine is
the formation of heterocyclic compounds such
as pyrimidines, imidazoles and oxazoles. Guani-
dine condenses with bifunctional compounds
such as diketones, acetoacetic acid esters, and
malononitrile [109-77-3], eliminating ammonia
or water to form 2-aminoheterocycles, for ex-
ample:
1.2. Production
No practical method exists for the direct syn-
thesis of free guanidine. All major manufac-
turing processes therefore involve the produc-
tion of guanidine salts by reaction of the ap-
propriate ammonium salt with compounds con-
taining the NCN group. At present, only dicyan-
diamide [461-58-5] (→ Cyanamides, Chap. 3),
cyanamide (→ Cyanamides, Chap. 2), and urea
[57-13-6] (→ Urea) are used for large-scale pro-
duction of guanidine salts.
1.2.1. Guanidine Salts from Dicyandiamide
Dicyandiamide is by far the most important raw
material for the production of guanidine salts.
Earlier processes conducted in acidic aqueous
solution with guanylurea as an intermediate [5]
have been abandoned. At present, guanidine
salts are manufactured by fusing dicyandiamide
with ammonium salts, with biguanide [56-03-1]
as an intermediate:
When carried out in batches in open stain-
less steel vessels at atmospheric pressure, reac-
tion begins above 130 – 140 ◦ C and becomes
exothermic at 170 ◦ C. The temperature is al-
lowed to rise to 210 – 230 ◦ C and is maintained
Table 1. Physical Properties of Guanidine Salts

Chloride Nitrate Carbonate Dihydrogen Hydrogen Sulfate Stearate Acetate Thiocyanate Aminosulfonate
phosphate phosphate

CAS registry number [50-01-1] [506-93-4] [593-85-1] [5423-22-3] [5423-23-4] [594-14-9] [26739-53-7] [593-87-3] [593-84-0] [51528-20-2]
Mr 95.54 122.09 180.17 157.07 216.22 216.1 343.36 119.13 118.16 156.2
mp, ◦ C 185 215 >190 a 130 246 >280 78 >227 117 127
d (25 ◦ C) 1.344 1.436 1.251 1.684 1.481 1.29 1.026 1.45 1.68
pH of aqueous solution 4.8 4.9 11.2 3.9 8.1 9.6 10 5 7
(20 wt %, 25 ◦ C)
Solubilityb , g per 100 g of
c
Water 228 20 50 230 23 ca. 270 115 160 120
90 ◦ C 450 148 80 410 160 ca. 400 160 ∞
Ethanol 30 1.4 0.03 <0.1 <0.1 0.02 135 8 65
70 ◦ C 57 8.6 0.1 <0.1 <0.1 0.05 ca. 25 170
Methanol 20 ◦ C 76 5.5 0.55 0.1 90
c
Acetone 0.05 0.1 0.02 <0.05 <0.05 <0.03 0.24 105
c
Benzene <0.05 0.05 0.01 <0.05 <0.05 <0.05 0.38 0.4
DMFd 19.5 6.1 0.02 0.05 0.21 15
a
Decomposes.
b
Unless otherwise stated, t = 30 ◦ C.
c
Trace.
d
Dimethylformamide.
Guanidine and Derivatives
3
4 Guanidine and Derivatives
within this range until the reaction has reached
completion. The molten mass is then dissolved
in water or mother liquor; insoluble triazine by-
products are filtered off. The guanidine salt is
crystallized by cooling or concentration of the
filtrate, centrifuged, washed, and dried.
Large-scale production of guanidine salts
such as guanidine nitrate is performed contin-
uously [6] (see Fig. 1).
Dicyandiamide (85 parts) and ammonium
nitrate [6484-52-2] (180 parts) are mixed and
dosed by a screw into a heated stirring vessel
where the mixture is melted down. The melt is
then run into a cascade of two further vessels
where the main reaction occurs. The hot molten
mass is subsequently dissolved in mother liquor
to give a warm salt solution, which is pumped
through a filter (to remove solid triazines) and
cooled in a continuously operating crystallizer.
The crystallized guanidine nitrate is centrifuged,
dried, and stored. This process is conducted on
a technical scale for guanidine nitrate, hydro-
chloride, and sulfamate. The yield of pure salt
is normally ca. 90 – 95 %. By solidifying the
molten mass on a cooling conveyor belt im-
mediately after it leaves the reaction cascade, a
crude product can be obtained containing ca. 91
– 92 % guanidine salt and 3 – 5 % ammonium
salt, together with small amounts of dicyandi-
amide and triazines.
Other processes involve the reaction of di-
cyandiamide, ammonium salts, and ammonia in
aqueous solution or in liquid ammonia under
pressure [6]. These processes are not industri-
ally important.
1.2.2. Guanidine Salts from Cyanamide
Cyanamide is used mainly for the production of
substituted guanidines (see Chap. 2). For simple
guanidine salts, calcium cyanamide [156-62-7]
is industrially important only in the production
of guanidine nitrate [9].
Calcium cyanamide is mixed with mother
liquor (from guanidine nitrate crystallization)
and concentrated ammonium nitrate solution,
and reacted at 120 ◦ C. An aqueous solution
of ammonium carbonate [506-87-6] is subse-
quently added to precipitate calcium carbonate.
The solids are separated by concentration and
filtration. The guanidine nitrate solution is neu-
tralized with nitric acid, freed of precipitated
sulfur by filtration, and of noxious gases such
as hydrogen sulfide by stripping, and worked up
as described above. Although this process gives
good yields, it is technically very complicated
and thus susceptible to breakdowns.
In modern cyanamide processes an aque-
ous solution of an ammonium salt and some
free ammonia is heated in a stirred autoclave
to 120 – 140 ◦ C [10]. Aqueous cyanamide so-
lution is then added slowly, and the reaction is
carried out at 0.5 – 1.5 MPa. After being cooled
to <100 ◦ C, the solution can be worked up as
usual. This method is used particularly to make
guanidine salts that cannot be produced effi-
ciently in a fusion process, e.g. guanidine car-
bonate [95, 96].
1.2.3. Guanidine Salts from Urea
Especially for guanidine nitrate, many attempts
have been made to produce guanidines from urea
feedstocks because of the cost advantage com-
pared to calcium carbide/calcium cyanamide
feedstocks. Melting urea with ammonium ni-
trate in presence of a silica catalyst at 120-200◦ C
gives guanidine nitrate in high yield according
to the following equation [11 – 14]
2H2 N−CO−NH2 +NH4 NO3 →
H2 N−C (NH) −NH2 ·HNO3 +CO2 +2NH3
Reaction safety hazard problems, difficulties re-
cycling off-gases and the ammonium nitrate ex-
cess, and problems with the re-usage of the spent
catalyst have prevented to date from large scale
realization of this process.
Guanidine carbonate is formed from urea as
a byproduct of some melamine [108-78-1] pro-
duction processes. It can be isolated from the
melamine mother liquor by heating (to remove
ammonia and carbon dioxide, and precipitate
the remaining melamine) and filtering. After
further concentration, the liquor is cooled and
the crystallized guanidine carbonate is separated
[15]. Although the removal of byproducts is
rather expensive, significant amounts of guani-
dine carbonate are isolated in this way by certain
melamine producers, mainly to minimize the
waste from melamine production which would
otherwise have to be burned or buried.
 Guanidine and Derivatives 5

Figure 1. Production of guanidine nitrate

a) Mixer; b) Metering bunker with screw; c) Melting vessel; d) Reaction vessels; e) Dissolving tank; f) Pump; g) Filter press;
h) Crystallizer; i) Centrifuge; j) Dryer; k) Storage bunker

1.2.4. Other Processes direct mixing and controlled heating of the pure
compounds [19].
Many processes for the production of guanidine This method gives guanidine salts of very
salts are mentioned in the literature: e.g., from high purity (depending on the raw materials),
urea and carbon disulfide; from urea, sulfur diox- because the only byproducts are carbon dioxide
ide, and ammonia; from carbon disulfide and and water, which are lost in the vapor.
ammonia; from carbon dioxide, ammonia, and
sulfur dioxide; from ammonium thiocyanate; or
from thiourea. None of these methods is used on
an industrial scale. For details, see [1, 5 – 8].
1.3. Environmental Protection
Guanidine hydrochloride can be made from
Apart from the ecological aspects of the produc-
cyanogen chloride upon reaction with NH3 in
tion of raw material (e.g., calcium cyanamide),
absence of a solvent at 140-220◦ C [16]. Guani-
guanidine production itself causes few environ-
dine salts of weak acids or anions that do not
mental problems. Ammonia, the only volatile
form stable ammonium salts can be manufac-
byproduct, must be removed by proper ventila-
tured via the free guanidine base. The latter is
tion and burned or recycled. Solid byproducts
prepared by reaction of a suitable guanidine salt
are mainly nontoxic melamine salts that can be
with a strong base, whose cation can be precip-
worked up (for applications, see → Melamine
itated with the anion of the guanidine salt. Such
and Guanamines), deposited, or burned.
reactions are usually carried out in alcohol solu-
At moderate concentration, guanidine and its
tion [17]. To obtain alkali-free guanidine solu-
common salts are nontoxic to microorganisms,
tion, guanidine carbonate or phosphate is reacted
but nitrification is rather slow [20]. Wastewater
in water with calcium hydroxide. After removal
containing guanidine can therefore best be re-
of the precipitated salt, the free guanidine base
moved by slow addition to a sewage plant that
can be isolated by careful vacuum distillation of
does not receive too many other nitrogen-con-
the solvent. A further possibility is addition of
taining compounds.
acid or acid anhydride to give the desired gua-
nidine salt. As an example, guanidine silicate
is produced in this manner from guanidine car-
bonate, calcium hydroxide, and amorphous sil- 1.4. Quality Specifications
ica [18].
A good way to prepare various guanidine Guanidine salts are normally available in pure
salts of strong or moderate acids, such as stearic (98.5 – 99.5 %) grade as white crystalline sub-
acid, in smaller amounts is to react guanidine stances containing some ammonium salts (0.3
carbonate with acids or anhydrides. This reac- – 0.6 %), triazines (0.2 – 0.4 %), water (0.1 –
tion can be carried out in aqueous solution or by 0.3 %), and possibly anticaking agent (SiO2 ,
6 Guanidine and Derivatives
0.2 – 0.4 %). Technical grades are also mar-
keted for some purposes as white to yellow-
ish lumps, granules, or powder, with 91 – 96 %
guanidine salt, 2 – 5 % ammonium salt, and 1
– 3 % triazines. Some salts are also available as
aqueous solutions, e.g., guanidine hydrochloride
(60 %), sulfamate, dihydrogen phosphate, or sil-
icate (each 50 %).
High-purity grades for specific applications
are available for guanidine thiocyanate and gua-
nidine hydrochloride. For example, solutions of
guanidine hydrochloride can be obtained as iron-
free (Fe < 0.1 ppm) or low absorbance products
(ε225 < 0.1).
1.5. Analysis
Nowadays guanidine salts are assayed routinely
by cation chromatography with conductivity de-
tection [21]. Besides other methods such as spec-
troscopic and colorimetric methods, guanidine
salts were formerly analyzed gravimetrically by
precipitation as the picrate [22].
1.6. Storage and Transportation
Guanidine salts are packed in polypropyl-
ene bags, drums with polyethylene lining, or
polypropylene big bags. If dry storage is avail-
able, guanidine salts can be stored for an unlim-
ited period. Caking of the guanidine salts how-
ever can be serious, leading to a single block of
product within a few months. Anticaking agent
can be added to reduce caking. Solutions must
be stored and shipped in plastic or coated steel
vessels to avoid corrosion. Cooling of aqueous
solutions may cause precipitation of the guani-
dine salt.
Guanidine nitrate is a dangerous commod-
ity according to transportation regulations and
is classified, along with other nitrates, as a sub-
stance that has oxidizing and ignitable properties
(class 5.1., 22c, UN 1467). For guanidine hydro-
chloride no declaration is necessary for trans-
port.
1.7. Legal Aspects
Within the European Union, guanidine hydro-
chloride and guanidine nitrate must be labeled
as hazardous substances as follows: guanidine
hydrochloride labeled with the hazard symbol
Xn (harmful), R 22 (harmful if swallowed), R
36 – 38 (irritating to eyes and skin), S 22 (do
not breathe dust); guanidine nitrate is provision-
ally labeled by the manufacturer with the hazard
symbol Xn , R 22, R 36, and S 26.
Guanidine perchlorate [10308-84-6] and pi-
crate [4336-48-5] are classified in the Federal
Republic of Germany as explosives according
to the Explosives Act (Sprengstoffgesetz). Han-
dling and storage of these salts are, therefore,
subject to special safety regulations prescribed
by this act [23] (→ Explosives).
Although the act does not specifically men-
tion pure guanidine nitrate (or nitroguanidine),
some mixtures of these substances with other
materials (e.g., potassium nitrate, ammonium
dichromate, or chlorinated hydrocarbons) are
also classified as explosives [23]. The export of
guanidine nitrate or nitroguanidine is controlled
by special regulations depending on the country
of destination.
1.8. Uses
1.8.1. Pharmaceuticals
Guanidine is a valuable intermediate in the syn-
thesis of a variety of pharmaceuticals. Important
industrial processes based on guanidine are, for
example, the synthesis of sulfonamides such as
Sulfaguanidine [57-67-0] [24], Sulfamethazine
[57-68-1] [25], Sulfadiazine [68-35-9] [25], and
related compounds like Pyrimethamine [58-14-
0] [26] and Trimethoprim [738-70-5] [27]. In
addition, purine derivatives such as Triamterene
[396-01-0] [28], Methotrexate [59-05-2] [29], or
Folic acid [59-30-3] are manufactured from gua-
nidine. More recently, this list of purines, based
on guanidine as a building block, has been ex-
tended to include commercially available antivi-
ral agents, e.g., Abacavir [188062-50-2], Pen-
ciclovir [145839-78-7] and Retrovir [256500-
90-0]. Many syntheses involve 2-aminopyrimi-
dines as intermediates. Promising acylguanidine
cardioprotectants are synthesized from guani-
dine salts. Monoacylguanidines, e.g., Cariporide
[159138-80-4], are effective Na+ /H+ -exchange
inhibitors [30]. The guanidine used is generally
prepared in situ by reacting salts such as guani-

dine nitrate, hydrochloride, or carbonate with a
strong base such as sodium methoxide.
1.8.2. Plant Protection
Guanidine salts are important building blocks
for the syntheses of various classes of pesti-
cides. The sulfonylurea herbicides, developed
by DuPont, often contain a 2-amino-4,6-dimeth-
oxypyrimidine fragment derived from guani-
dine. Prominent examples of these active ingre-
dients which inhibit the syntheses of essential
amino acids by blocking the enzyme acetolactate
synthase are Bensulfuron-methyl [83055-99-6]
(Dupont) and Halosulfuron-methyl [100784-20-
1] (Monsanto, Nissan).
Another class of crop-protection agents
which are derived from guanidine compounds
are the neonicotinoids, which all contain a
nitroguanidine fragment. Examples are Imida-
cloprid [138261-41-3] (Bayer), Thiamethoxam
[153719-23-4] (Syngenta) and Clothianidine
[210880-92-5] (Takeda, Bayer).
1.8.3. Cosmetics
Guanidine carbonate is used industrially as a
nontoxic, highly soluble component of hair care
products.
1.8.4. Textile Impregnation, Flame
Retardants, Paper and Resin Manufacture
Guanidine hydrochloride is used for textile im-
pregnation as an antistatic agent. Guanidine
phosphates are used as flame retardants for
cellulosic products like wood, paper, textiles,
and laminates. They decompose above 300◦ C
forming noncombustible gases together with
polymetaphosphates [31]. The highly soluble
primary guanidine phosphate is used for di-
rect impregnation, while the lesser soluble sec-
ondary phosphate often is incorporated in, e.g.,
bonding resins for laminates. Guanidine sulfa-
mate has large-scale application in the manu-
facture of flame-retardant papers, especially in
Japan where paper walls are common. Guani-
dine stearate is used as an emulsifier and surface-
modifying agent in the production of resin coat-
ings and papers.
Guanidine and Derivatives 7
1.8.5. Propellants and Explosives
Guanidine nitrate is used nowadays in many
non-azide formulations for gas generators in
automobile airbag applications [32 – 34]. As a
constituent of these pyrotechnic mixtures, gua-
nidine nitrate is not regarded as an oxidizer, but
as a gas-generating fuel due to its net oxygen
demand upon combustion. Guanidine nitrate is
used in large amounts to produce nitroguanidine,
which is employed widely in the manufacture
of propellants and explosives. This process in-
volves the reaction of guanidine nitrate with con-
centrated sulfuric acid.
Guanidine perchlorate and picrate have been
tested as explosives but are of no industrial im-
portance.
1.8.6. Biotechnological Applications of
Guanidine Salts
Guanidine hydrochloride and thiocyanate are
among the most potent protein denaturants
known [35], readily surpassing urea, the other
widely employed denaturing agent, in effec-
tiveness for most applications. The physico-
chemical mechanism involves strong hydrogen
bonding to guanidine, modulating structure and
solvent properties of water [36]. Their primary
application appears to be in the isolation of pro-
teins and enzymes, particularly from genetically
modified microorganisms. After successful ma-
nipulation of the genetic constitution of a mi-
croorganism, the microbial cell begins to pro-
duce the protein of interest, which then accumu-
lates in special cellular compartments known as
inclusion bodies. To isolate these proteins, they
must be released from the inclusion bodies and
separated from other cellular constituents.
Traditionally, urea (6 – 9 M) has been used
for this purpose, but guanidine salts, partic-
ularly the hydrochloride (2 – 6 M), are gain-
ing acceptance as substitutes with distinct ad-
vantages [37]. For example, guanidine hydro-
chloride tends to cause less protein inactivation
[37], partly because lower concentrations can
be used, compared with urea. Furthermore, gua-
nidine hydrochloride is removed from the ex-
tracted protein after denaturing simply by dilu-
tion [38]. The use of guanidine salts generally
8 Guanidine and Derivatives
results in higher yields of extracted protein than
is the case with urea.
In addition no protein modification is ob-
served with guanidine hydrochloride as is the
case with cyanate present in urea solutions which
leads to carbamoylated lysine in the protein of
interest.
Furthermore, recombinant Protein A, bound
to a chromatography support for immunoaffinity
purification of humanized monoclonal antibod-
ies, is effectively regenerated between purifica-
tion batches (so-called column stripping).
Guanidine salts have attained an unrivaled
position in the extraction and purification of
biologically active RNA [39, 40], because of
their strong denaturing properties. Guanidine
thiocyanate is often the salt of choice and is
used frequently in combination with, or in place
of, phenol for the extraction of RNA [41, 42].
The above-mentioned advantages make guani-
dine salts particularly attractive for the isolation
of substances such as interferons [37, 43], inter-
leukins [44], and the blood factors tissue plas-
minogen activator (tPA) and urokinase, as well
as humanized monoclonal antibodies like Her-
ceptin or ReoPro.
1.9. Economic Aspects
The worldwide production capacity of guani-
dine salts is estimated to be several tens of thou-
sands of tons per year. This figure includes sig-
nificant spare capacity for the production of gua-
nidine nitrate. The exact capacity and output of
these plants is not known. In most cases, the
amount produced is far less than capacity and
is used exclusively as captive raw material for
the production of nitroguanidine. Apart from
this, worldwide annual consumption of guani-
dine salts is estimated to be several thousands
of tons. The main producers are located in Ger-
many and Japan. Smaller amounts are produced
in Austria, India, and the People’s Republic of
China.
2. Derivatives
For Cyanoguanidines (Dicyandiamides) see →
Cyanamides, Chap. 3.
2.1. Nitroguanidine [45 – 47]
Nitroguanidine [556-88-7], CH4 N4 O2 , M r
104.07, is a very weak base that forms salts
only with strong acids. Its solubility in water at
20 ◦ C (100 ◦ C) is 0.27 % (7.6 %). It decomposes
at 220 ◦ C.
Nitroguanidine is made by treating guanidine
nitrate with concentrated sulfuric acid, fuming
nitric acid, or both. The reaction of nitroguani-
dine with amines gives substituted nitroguani-
dines [45].
Nitroguanidine (available from Nigu
Chemie) is used as a component in triple-based
propellants, impact-insensitive military ammu-
nition and as a gas generator in automotive
airbag applications [48]. Nitroguanidine is also
used in anticorrosive phosphate coatings [49].
2.2. Aminoguanidine [50 – 53]
Aminoguanidine [79-17-4], CH6 N4 , M r 74.09,
is a base that forms salts with both inorganic
and organic acids [50]. It is soluble in water and
ethanol. Preparation of the nitrate [10308-82-4],
CH6 N4 · HNO3 , involves the risk of explosion
[54].
Free aminoguanidine is stable for only a short
time; therefore, it is marketed in the form of its
stable salts. Commercially, aminoguanidine is
offered as the bicarbonate salt [2582-30-1], a
white powder of usually 99 % assay. The water
solubility at room temperature is low (< 5 g/L).
It is offered by most world-scale hydrazine pro-
ducers (→ Hydrazine). Other salts can be pre-
pared from the bicarbonate by reaction with acid.
Aminoguanidine is prepared from hydrazine
and aqueous cyanamide solution. Processes
based on the reduction of nitroguanidine have
no industrial significance.
 Guanidine and Derivatives 9

Uses. Aminoguanidine can act as both a hy-

drazine and a guanidine derivative; it is par-
ticularly suitable for the synthesis of various
nitrogen-containing heterocyclic compounds
such as pyrazoles, 1,2,4-triazoles, thiadiazoles,
tetrazoles, pyrimidines, 1,2,4-triazines, thiadia-
zoles, and tetrazines [53].
Aminoguanidine salts can be used for remov-
ing undesired aldehydes by formation of hydra-
zones, e.g., in oxidation processes or in polymer Salts and derivatives of aminoguanidine are
syntheses with methacrylic acid. recommended as stabilizers for poly(vinyl chlo-
Cyclization with formic acid produces 3-ami- ride), as flame retardants, for coatings of phar-
no-1,2,4-triazole [61-82-5]: maceutical microspheres and as textile auxil-
iaries.

2.3. Diamino- and Triaminoguanidine

This compound is an important herbicide
(Amitrole, ATA), which has a synergistic action
with many nonselective herbicides. Some com-
mercially available agrochemicals are based on
aminoguanidine, e.g., the fungicide Meferim-
zone [89269-64-7], 4,6-dimethyl-2-[1-(2-meth-
ylphenyl)ethylidenehydrazino]-pyrimidinone.
3-Amino-1,2,4-triazole is also used for the
preparation of red and yellow cationic triazole
dyes such as C.I. Basic Red 22 and C.I. Basic
Yellow 25, for poly-(acrylonitrile) fibers (→
Methine Dyes and Pigments). Pharmaceutical
applications include Lamotrigine, 3,5-diami-
no-6-(2,3-dichlorophenyl)-1,2,4-triazine, an an-
ticonvulsant and glutamate inhibitor (Glaxo-
Wellcome), and the treatment of type II diabetes
with aminoguanidine [56].
Aminoguanidine reacts with nitrous acid in
acidic aqueous environment to form 5-amino-
(1H)-tetrazole [4418-61-5] via guanylazide as
an intermediate, the former being used a a gas
generator, e.g., for automotive airbags [57, 58].
Under neutral pH conditions, diazotization of
aminoguanidine leads to 4-(1H-tetrazol-5-yl)-
1-tetrazene-1-carboxamidine [539-57-1], used
as a component for shock sensitive explosive
primers [59]. Diazotization in glacial acetic acid
gives 1,3-di-(tetrazol-5-yl)-triazene [56929-36-
3] [60].
[51, 52, 61]
Diaminoguanidine. Development of the
chemistry of N,N  -diaminoguanidine [4364-
78-7], CH7 N5 , M r 89.10, has been hampered
by the lack of convenient methods for synthe-
sizing it in reasonable purity; a summary of the
available methods is given in [52]. In preparing
of the hydrochloride [38360-74-6] by reaction
of hydrazine with cyanogen chloride in a molar
ratio of 2 : 1, the formation of byproducts can be
suppressed if the reaction is carried out in sat-
urated aqueous sodium chloride solution: yield
71 %, mp 170 – 176 ◦ C [62].
Diaminoguanidine is used in the preparation
of robenidine [25875-51-8], the hydrochloride
[25875-50-7] of which is an anticoccidial agent
for poultry.
Triaminoguanidine. Salts of N,N N -
triaminoguanidine [2203-24-9], CH8 N6 , M r
104.11, are formed by heating the corresponding
guanidine salts with hydrazine (molar ratio 1 :
10 Guanidine and Derivatives
3) in aqueous solution or in alcohol. The triami-
noguanidine base can be liberated from its salts
by treatment with sodium hydroxide and can be
crystallized from aqueous dimethylformamide.
Triaminoguanidine nitrate (TAGN) [4000-
16-2] is an effective explosive [64]. It is useful
as a component of propellants.
2.4. Organoguanidines
A large number of organoguanidine derivatives
are known. The many methods of preparation are
described in detail in an excellent monograph on
carbon dioxide derivatives [65, 66].
The addition of amines, polyamines, hy-
drazines, or hydroxylamines to cyanamides is
one of the most common industrial processes for
the synthesis of guanidines. Cyanamide [420-
04-2] is available as a 50 % aqueous solution or
in crystalline form; substituted cyanamides can
be obtained from amines and cyanogen chloride
(→ Cyanamides).
The classical preparation of guanidines by the
action of amines on S-alkylisothioureas is versa-
tile and suitable also for the preparation of cyclic
compounds. The elimination of alkanethiol by-
products is, however, a disadvantage.
A method for synthesizing di- and trisub-
stituted guanidines is the reaction of oxidized
thioureas with nucleophilic amines [67].
An advanced reagent to produce N  ,N  -bis-
protected guanidines from various amines is
N,N  -di-BOC-N  -triflylguanidine (“Goodman-
reagent”, [207857-15-6]) [68].
2.4.1. Alkylguanidines
Monosubstituted and N,N-disubstituted com-
pounds, including guanidinocarboxylic acids
(e.g., creatine [57-00-1]), are produced industri-
ally by the reaction of cyanamide with the cor-
responding amines or aminocarboxylic acids.
However, l-arginine (→ Amino Acids), the
most frequently found guanidino compound in
nature, can be best isolated from proteins.
For convenient guanylation (amidination) of
primary alkylamines and amino acids without
formation of methanethiol, S-methylisothiourea
sulfate (2 : 1) [867-44-7] can be replaced by
commercially available O-methylisourea sulfate
(2 : 1) [52328-05-9]. Thus, methylguanidine sul-
fate (2 : 1) [598-12-9] and ethylguanidine sulfate
(2 : 1) [3482-86-8] are obtained in quantitative
yield by the action of methylamine and ethy-
lamine, respectively, on O-methylisourea sulfate
in aqueous solution at 50 ◦ C:
For steric reasons, O-methylisourea salts re-
act preferentially with primary amines and are
particularly suitable for selective guanylation of
the terminal amino groups of polyamines. O-
Methylisourea sulfate (available from Degussa
AG) is a convenient guanylating agent and is
also used on an industrial scale for the synthe-
sis of heterocyclic compounds, e.g., benzimid-
azole anthelmintics and the antibacterial agents
pipemidic acid [51940-44-4] and piromidic acid
[19562-30-2].

Guanidine Bases. Free alkylguanidines are
strong bases that are more stable than unsubsti-
tuted guanidine.
N,N,N ,N -Tetramethylguanidine (TMG)
[80-70-6], C5 H13 N3 , M r 115.18, is a stable,
unusually strong base, pK a 13.6 (25 ◦ C), with a
free imino group. It is a colorless to light-yellow
liquid, miscible with water and common or-
ganic solvents: 0.92 g/cm3 (25 ◦ C), bp 160 ◦ C,
vapor pressure 0.03 kPa (25 ◦ C). Prepared from
cyanogen chloride and dimethylamine in a 1 : 2
molar ratio [69], TMG is used as a polyurethane
foam catalyst, in the preparation of pigments for
color photography, and in steroid synthesis. It is
available from Degussa AG and Lonza.
Undiluted N,N,N ,N -tetramethylguanidine
strongly irritates the eyes, skin, and mucous
membranes. Its LD50 is ca. 850 mg/kg (rat,
oral).
Salts of tetramethylguanidine [70] or salts of
cyclic, peralkylated guanidines [71] have been
proposed as ionic liquids for solvent use in
“green” chemical reactions.
Short-Chain Alkylguanidines as Build-
ing Blocks in Synthesis. Some monosubsti-
tuted and N,N-disubstituted derivatives are used
as intermediates for the preparation of crop-
protecting agents.
Pyrimidines can be prepared by condensation
of alkylguanidines with a 1,3-difunctional C3
fragment. Cyclization of alkylguanidines with
2-alkylacetoacetic acid esters produces fungi-
cidally active 5-alkyl-2-alkylamino-4-hydroxy-
6-methylpyrimidines. The systemic fungicides
bupirimate [41483-43-6] and dimethirimol
[5221-53-4], developed by ICI, belong to this
class of compounds.
N,N-Diethylguanidine [18240-93-2] and
N,N-dimethylguanidine [6145-42-2] are used as
an N−C−N building block for the pyrimidine
Guanidine and Derivatives 11
insecticides pirimiphos-methyl [29232-93-7],
pirimiphos-ethyl [23505-41-1], and pirimicarb
[23103-98-2]. Pirimiphos-methyl has proved
particularly effective for the control of storage
pests.
Biologically Active Compounds. Higher
alkylguanidines and polyguanidines, because of
their fungicidal and antibacterial action, are eco-
nomically important as fungicides in agriculture
or as antimicrobial agents in disinfectants and
industrial biocides [72, 73].
n-Dodecylguanidine acetate [2439-10-3],
Dodine, used primarily for the control of apple
and pear scab, exhibits both protective and cura-
tive action. Dodine is also a bacteriostatic agent.
Dodecylguanidine derivatives are recommended
as effective biocides for controlling biological
growth in industrial coolant systems.
Other broad-spectrum microbiocidal uses
based on alkylguanidine salts include disinfec-
tion, sanitation, preservation, and control of
Desulfovibrio desulfuricans corrosion [73].
Guazatine, prepared by the guanylation of
aliphatic diamines and polyamines, is used for
cereal seed dressing. It is also used as a posthar-
vest dip in citrus growing. Guazatine is effective
against wood-discoloring fungi and, together
with quaternary ammonium compounds, is a
constituent of wood preservatives.
Based also on guazatine, contact fungicides
were developed which control, e.g., the growth
of Septoria nodorum in wheat [74].
Iminoctadine triacetate is a broad-spectrum
contact fungicide, developed by Dainippon Ink
and Chemicals (DIC); the active ingredient is
the triacetate salt of 1,1 -[iminobis(octamethy-
lene)]diguanidine [57520-17-9]. The product is
used in Japan primarily for the control of top
fruit (tree fruit) and citrus diseases; in Western
Europe, good action has been achieved against
leaf spot and glume blotch in winter wheat [75].
Other Uses. Guanidinium salts of unsatu-
rated fatty acids are used as corrosion inhibitors
[76]. Alkylguanidines linked to a styrene poly-
mer matrix have been proposed as phosphate
scavengers for pharmacological treatment of hy-
perphosphatemia [77].
2.4.2. Arylguanidines
Monoarylguanidines can be prepared by
heating aromatic amine hydrochlorides with
12 Guanidine and Derivatives
excess cyanamide in aqueous solution. Aryl-
biguanides are common byproducts. Phenylgua-
nidines can be precipitated from the reaction
mixture as a carbonate or bicarbonate salt [78].
Phenylguanidine has found application in the
production of pyrimidine fungicides like Cypro-
dinil [121552-61-2] [79], Pyrimethanil [53112-
28-0] [80], and Mepanipyrim [110235-47-7]
[81].
From the group of 2-guanidinoanilides with
anthelmintic properties, febantel [58306-30-2]
(Rintal), supplied by Bayer, has emerged as an
effective broad-spectrum anthelmintic; it is used
to treat nematode infections in domestic ani-
mals.
The guanidine derivative linogliride fumarate
(1 : 1) [78782-47-5] is a new oral antidiabetic,
developed by McNeil. It can be prepared by the
Maryanoff process [67].
Diarylguanidines. N,N -Diphenylguanidine
(DPG) [102-06-7] and N,N -di-o-tolylguanidine
(DOTG) [97-39-2] are used as vulcanization ac-
celerators. Because of their low activity they do
not play a major role as primary accelerators;
however, they are very important in combina-
tion with other accelerators. Diarylguanidines
can be used as secondary accelerators for thia-
zoles, sulfenamides, thiurams, and dithiocarb-
amates; the most frequently used combination
is with mercapto accelerators. These accelera-
tors and the guanidine produce an extraordinary
increase in the degree of cross-linking and the
rate of vulcanization; high mechanical values
(high tensile stress and elasticity) are achieved.
N,N  -Diphenylguanidine is the most important
of the three guanidines DPG, DOTG, and OTBG
(o-tolylbiguanide; see Section 2.5).
Both DPG and DOTG are prepared by re-
action of cyanogen chloride with aniline or o-
toluidine, respectively, in a molar ratio of 1 : 2.
Cyclic Derivatives. N,N -o-Phenylenegua-
nidine [934-32-7], 2-aminobenzimidazole,
C7 H7 N3 , M r 133.15, mp 231 – 232 ◦ C (de-
comp.), obtained by cyclization of o-phenylene-
diamine with cyanogen chloride or cyanamide,
is the nucleus for a number of compounds of
economic interest; for a review of 2-aminobenz-
imidazoles, see [82].
Several 2-(methoxycarbonylamino)benzim-
idazoles exhibit biological activity. Carben-
dazim (R = R = H) [10605-21-7] is an im-
portant systemic fungicide, while its deriva-
tive Benomyl (R = H, R R =R CO–NH–C4 H9 )
[17804-35-2] has been withdrawn from the mar-
ket recently.
Effective anthelmintics, mainly for veteri-
nary use, are:
Albendazole [54965-21-8] (R = S–C3 H7 , R = H)
Fenbendazole [43210-67-9] (R = S–Ph, R = H)
Flubendazole [31430-15-6] (R = CO–C4 H6 –p–F, R = H)
Mebendazole [31431-39-7] (R = CO–Ph, R = H)
Oxfendazole [53716-50-0] (R = SO–Ph, R = H)
Oxibendazole [20559-55-1] (R = O–C3 H7 , R = H)
Albendazole and flubendazole are also ef-
fective against worm infection in humans (→
Anthelmintics, Chap. 3.0.0.0.0.7). Substituted
2-(methoxycarbonylamino)benzimidazoles can
be prepared by cycloguanylation of the cor-
responding o-phenylenediamine derivatives
with N-methoxycarbonyl-S-methylisothiourea
[39259-32-0] or N-methoxycarbonyl-O-
methylisourea [40943-37-1].

2.5. Biguanide and Derivatives
Biguanide [56-03-1], C2 H7 N5 , M r 101.11,
mp 130 ◦ C (which decomposes violently at
142 ◦ C), is a moderately strong base (pK b 2.9).
It is readily soluble in water and ethanol, and in-
soluble in ether, benzene, and chloroform. The
free base decomposes gradually in aqueous so-
lution. Biguanide forms stable salts with most
acids.
Reviews of methods for the preparation of
biguanide can be found in [83, 84]. Biguanide
salts are prepared by the fusion of dicyan-
diamide with ammonium salts. [Dibiguanide
– copper(II)] sulfate, [Cu(C2 H7 N5 )2 ]SO4 , is
formed by heating dicyandiamide with ammo-
niacal copper sulfate solution to 90 – 110 ◦ C
in a pressure vessel [85]; it can be converted
by decomposition with hot 10 % sulfuric acid
or hydrogen sulfide to biguanide sulfate (1 :
1) [6945-23-9], C2 H7 N5 · H2 SO4 , or biguanide
sulfate (2 : 1) [49719-55-3], 2 C2 H7 N5 · H2 SO4
[85, 86].
Biguanide is used to prepare 6-substituted
2,4-diamino-1,3,5-triazines [84]. The reaction
of biguanide with esters to form guanamines is
catalyzed by sodium alkoxides.
Biguanides substituted at the N-1 posi-
tion are obtained by heating dicyandiamide with
aliphatic or aromatic amine hydrochlorides in
water, higher boiling alcohols, or in a melt reac-
tion.
N-substituted biguanide hydrochlorides have
found widespread application in pharmacology.
Buformin [692-13-7], Phenformin [114-86-3]
and Metformin [657-24-9] are used against type
II diabetes, the latter being sold in quantities of
more than 1000 tons per year worldwide (→ An-
tidiabetic Drugs, Chap. 3).
Guanidine and Derivatives 13
o-Tolylbiguanide (OTBG) [93-69-6],
C9 H13 N5 , M r 191.23, mp 144 ◦ C, is used as
a vulcanization accelerator in the same manner
as the guanidines DPG and DOTG (see Section
2.4.2.). An important use is in the preparation
of consumer articles that come in contact with
food and drinking water (Recommendation XXI
of the German Federal Department of Health).
o-Tolylbiguanide is also employed as a curing
agent with moderate reactivity for color-stable,
highly glossy or transparent epoxy resin powder
coatings.
The N-1,N-5-disubstituted biguanides can
be prepared by addition of amines to substituted
cyanoguanidines. A particularly convenient syn-
thesis of N1-alkyl-N-5-aryl biguanides involves
heating aliphatic cyanoguanidines with aromatic
amine hydrochlorides [87, 88]: the antimalarial
drug proguanil [500-92-5] is obtained as the hy-
drochloride [637-32-1] (Paludrine) by reaction
of isopropyldicyandiamide with 4-chloroaniline
hydrochloride in boiling water [87].
Chlorhexidine [55-56-1], 1,6-bis(4-chloro-
phenylbiguanido)hexane, C22 H30 Cl2 N10 , M r
505.45, mp 134 ◦ C, is a widely used an-
tiseptic (→ Disinfectants). It can be pre-
pared, for example, from 1,6-hexamethy-
lenebis(dicyandiamide) and 4-chloroaniline hy-
drochloride [89]. Chlorhexidine is used pri-
marily as its salts (e.g., the dihydrochloride
[3697-42-5], diacetate [56-95-1], and diglu-
conate [18472-51-0]) in disinfectants (disinfec-
tion of the skin and hands), cosmetics (additive
to creams, toothpaste, deodorants, and antiper-
spirants), and pharmaceutical products (preser-
vative in eyedrops, active substance in wound
dressings and antiseptic mouthwashes) [73].
Poly(hexamethylene biguanide) hydro-
chloride (PHMBG, [27083-26-7]) is a broad-
spectrum industrial biocide developed by ICI.
The most important uses are in surface disin-
fection in hospitals and the food and beverage
14 Guanidine and Derivatives
industry, and in the preservation of aqueous sys-
tems (i.e., aqueous solutions of organic prod-
ucts, such as cutting oils and domestic cleaning
agents) [73]. PHMBG also is used to make up
spa water and private swimming pools, where
it acts as a flocculant for organic biogenic col-
loids. Polymeric biguanide hydrochlorides with
broad antimicrobial action, very low toxicity,
and good skin tolerance are also contained in
preservatives for cosmetic formulations.
3. Toxicology and Occupational
Health
The guanidino group is low in acute toxicity and
is not associated with severe health hazards. No
mutagenic, carcinogenic, or teratogenic poten-
tial has been demonstrated for guanidine.
Free guanidine and its solutions exhibit
strong alkaline reactions. They must therefore
be handled like alkali metal hydroxides or alkox-
ides. Guanidine salts of weak acids (e.g., guani-
dine silicate) also have alkaline properties. An-
imal tests (rabbit) show that guanidine hydro-
chloride is a severe primary skin and eye ir-
ritant [7, 90]. In a similar test, guanidine ni-
trate produced mild to moderate eye irritation
[91]. Guanidine hydrochloride and guanidine ni-
trate did not show sensitizing properties in the
Buehler test [92, 93].
Toxicities of some guanidine salts (acute oral
LD50 , rat) are guanidine hydrochloride 1120
mg/kg, guanidine nitrate 1260 mg/kg, guani-
dine carbonate 1020 mg/kg, guanidine sulfa-
mate 2334 mg/kg, and guanidine stearate 7500
mg/kg. Further toxicological data for guanidine,
its salts, and derivatives can be found in [93, 94].
The toxicological properties of individ-
ual guanidine derivatives depend primarily on
the type of the substitutents. Commercially
available guanidines generally have relatively
low toxicity. The following are LD50 val-
ues (rat, oral) for some derivatives: aminogua-
nidine bicarbonate >5000 mg/kg; nitroguani-
dine 4650 mg/kg; N,N,N ,N -tetramethylguani-
dine ca. 850 mg/kg; n-dodecylguanidine ac-
etate 1000 mg/kg; N,N -diphenylguanidine 507
– 850 mg/kg; o-tolylbiguanide 1800 mg/kg.
Guanidine derivatives may, however, contain
amines as impurities, because amines are used
as starting material in the production of guani-
dines.
With the exception of nitroguanidine, cyano-
guanidines, and acylated guanidines, guanidine
derivatives are basic; the free bases can cause
irritation and corrosion of the skin, eyes, mu-
cous membranes, and respiratory tract. Skin and
eye contact with the strong free bases should be
avoided. The salts are less irritating than the free
bases. Exposure limits (MAK and TLV values)
have not been established.
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