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Glucose and Glucose-Containing Syrups

FRED W. SCHENCK, Consultant (retired), Sun City, Arizona 85373–1113, United States

1. Introduction and History . . . . . . . . . . . . . . . . 45 5.2. Production of Pure Crystalline Products . . . . 56


2. Properties of Glucose. . . . . . . . . . . . . . . . . . . 48 6. Glucose – Fructose Syrups . . . . . . . . . . . . . . 58
2.1. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 6.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.2. Physical Properties . . . . . . . . . . . . . . . . . . . . 48 6.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.3. Chemical Properties . . . . . . . . . . . . . . . . . . . 49 6.3. High-Fructose Syrups from Inulin. . . . . . . . . 60
3. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . 49 7. Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4. General Principles of Starch Hydrolysis . . . . 51 8. Legal Aspects. . . . . . . . . . . . . . . . . . . . . . . . . 61
4.1. Production and Properties of Acid Glucose 9. Storage and Transportation. . . . . . . . . . . . . . 62
Syrups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 10. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.2. Production and Properties of Acid – Enzyme 11. Economic Aspects . . . . . . . . . . . . . . . . . . . . . 63
Glucose Syrups . . . . . . . . . . . . . . . . . . . . . . . 54 12. Physiological Properties and Toxicology of
4.3. Production and Properties of Enzyme – Glucose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Enzyme Glucose Syrups. . . . . . . . . . . . . . . . . 54 References . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5. Production of Solid Glucose. . . . . . . . . . . . . . 56
5.1. Production of Total Sugars . . . . . . . . . . . . . . 56

1. Introduction and History to crystallization. However, despite the abun-


dance of glucose in nature, the disaccharide
The saccharides are among the most common sucrose has historically been the primary sweet-
organic compounds found in nature and glucose ener for humans. Sucrose is sweeter than
is by far the most abundant monosaccharide. D- glucose, and very pure crystals can be
Glucose (D-glucopyranose) [50-99-7], C6H12O6, recovered from syrups extracted from sugar
Mr 180.159, is the primary six-carbon sugar (hex- cane and sugar beets (! Sugar).
ose) found in the juice of most fruits and berries. Most glucose, on the other hand, is bound up
Starch (! Starch) and cellulose (! Cellulose, as starch, requiring complicated manufacturing
Section 3.2) are composed of anhydroglucopyr- processes to release its sweetness. The growth
anose units connected through a- and b-linkages, of the glucose sweetener industry has been
respectively, to form long-chain polymers. Thus, a based upon a classic response to market needs
considerable portion of the human diet is com- for improved purity and functionality.
posed of glucose in either the free or the poly- Pure glucose was first obtained from grape
merized state. juice by the German chemist A. S. M ARGGRAF in
When a-linked polymers of glucose (starch) 1747 [1]. PROUST was one of the first to precipitate
are ingested, acid and enzymatic processes con- a-D-glucose crystals from grape juice in 1801
vert these macromolecules to glucose in much [2]. The synonym for D-glucose, grape sugar,
the same way that it is made commercially. The owes its origin to this process.
digestive process begins in the mouth with the The first sweetener created from starch was
action of salivary amylase. Final digestion is the disaccharide maltose made in China about
accomplished by the action of numerous other 1000 B.C. by the enzymatic hydrolysis of rice
enzymes in the small intestine. [3]. By 1781, it was known in Europe that
D-Glucose was probably known to early hu- starches could be treated with acids to produce
mans because it appears as granules in honey due a soluble, sweet-flavored substance [4]. This

2012Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


DOI: 10.1002/14356007.a12_457.pub2
46 Glucose and Glucose-Containing Syrups Vol. 17

knowledge was little more than a laboratory In the United States in 1923, WILLIAM B.
curiosity until the Napoleonic Wars when the NEWKIRK (Corn Products Refining Company)
blockade of cane sugar imports from the West received a patent for developing a commercially
Indies provided incentive for the development feasible process for the production of pure crys-
of alternative sweeteners. talline glucose [7]. By careful control of the
In 1811, G. S. C. KIRCHOFF, who was looking conditions during the crystallization step, large,
for a substitute for gum arabic (used in the easily separable crystals could be produced
manufacture of porcelain), overcooked a economically and an industry was born.
mixture of potato starch and sulfuric acid [5]. Although glucose and glucose-containing
The sweet, syrupy substance that resulted syrups can have functional advantages over
earned him a lifetime pension of 500 rubles per sucrose (higher viscosity, greater solubility,
year from the Russian Emperor. bland flavor, etc.) in certain applications, the
KIRCHOFF recognized the commercial poten- unmatched sweetness of sucrose prevented
tial of his discovery and proceeded to improve glucose-containing syrups from capturing more
the process. He succeeded in preparing a syrup than about one-fifth of the caloric sweetener
that crystallized partially on standing, and from market in the United States. In many of its uses,
which a solid product (impure D-glucose) could sucrose in aqueous solution is treated with
be obtained by pressing the mass in cloth sacks. either acid or enzymes to produce invert syrup
This solid material contained large quantities of con-sisting of a 50 : 50 glucose – fructose
uncrystallized syrup and was quite impure. mixture (! Fructose, Section 2.1). Thus, in a
Nevertheless, serious attempts were made to highly converted glucose syrup, isomerization
manufacture the product on a large scale. How- of half of the glucose to fructose would make
ever, the defeat of Napoleon at Waterloo made starch-based syrups about as sweet as those
cane sugar available once again and the venture made from sucrose.
was abandoned. Glucose isomerization under alkaline condi-
The French chemist SAUSSURE determined tions (see Section 2.3), which increases sweet-
that the acid conversion of starch was achieved ness somewhat, results in a highly colored
through a hydrolytic reaction that cleaved the product with off-flavor. In 1957, a xylose isom-
linkages between the anhydroglucopyranose erase enzyme was reported to convert glucose
units in starch by adding one molecule of water to fructose [8], and a US patent was issued to
to each unit to produce the basic building the Corn Products Refining Company in 1960
block, D-glucose. It was also recognized that [9]. However, no industrial activity was imme-
candies manufactured with glucose syrups were diately pursued in the United States, and glucose
not cloy-ingly sweet as were those made from isomerase research shifted to Japan in the 1960s
sucrose, thus allowing delicate flavors to reach [10].
the palate. As a result, the ‘‘starch sugar’’ Once the economical enzymatic conversion
industry devel-oped in Europe (especially in of glucose to fructose had been demonstrated
Germany) and in the United States [6]. by the Japanese, the technology moved back to
Early efforts to improve the quality of ‘‘starch the United States. In 1965, the Clinton Corn
sugars’’ were attempts to control the nonspecific Proces-sing Company (United States) and the
nature of the acid hydrolysis. The market needed Japanese Agency of Industrial Science and
purer glucose, but early commercial production Technology worked together to commercialize
(1880 – 1920) of crystalline glucose required fructose-con-taining syrups made in the United
either repeated crystallization steps or crystalli- States by enzymatic isomerization of glucose.
zation from nonaqueous solvents. The only solid At about the same time, the first batchwise
form of glucose available in quantity at low price production began in Japan.
at this time was a cast product; starch was acid The degree of enzymatic isomerization of
converted to as high a degree as possible, evapo- glucose to fructose depends on a number of
rated to a thick syrup, and poured into molds operating parameters. Because higher fructose
where it hardened into solid blocks. It was sub- content is desired, higher operating temperature
sequently removed from the molds, chipped into and/or increased reaction time is required. How-
small pieces, and sold. ever, both of these process conditions reduce
Vol. 17 Glucose and Glucose-Containing Syrups 47

the effective enzyme productivity. Although


enzymatic isomerization of glucose to fructose
in excess of 50 % db (dry basis) is possible,
conversion to a 42 % db fructose content was
chosen as the best balance between increased
sweetness and process economics. The first
com-mercial 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 Figure 1. Per capita US sweetener consumption by type
was not sweet enough to satisfy the demands of 1965 – 2005
the most important U.S. soft drink producers.
By use of chromatographic separation techni-
ques, the 42 % fructose syrup was enriched to a The first large-scale production of 55 %
fructose content in excess of 90 % db. Blending fruc-tose syrup began in 1978; by 1984,
this enriched syrup with 42 % fructose syrup, fructose syrups derived from glucose had
the sweetness level of total invert syrup was replaced sucrose in nearly 100 % of the soft
matched at 55 % fructose content. More than 50 drinks pro-duced in the United States,
% fructose was required because the various substantially reducing sucrose consumption.
glucose polymers remaining in the syrup, due to Today, glucose-based sweeteners account for
incomplete starch hydrolysis have a lower more than half of the total caloric sweeteners
sweetening power. consumed in the United States (see Fig. 1)[12].
North America, led by the United States, is the
dominant leader in the production and consump-
tion of glucose – fructose syrups, consuming 74.1
% of the world production of 11.8 106 t (dry
Table 1. Distribution by industry of crystalline glucose, glucose – basis) today, followed by Asia and Oceania at
fructose, and glucose-containing syrups in the United States (in 103 14.8 %, with European consumers using 7.1 %
t, commercial basis) [11]
and Latin America and Africa accounting for the
Year Baking Beverage Canning Confectionery Dairy Total remaining 4 % [13]. This market dominance is
Crystalline glucose
expected to continue for the forseeable future the
1965 177 9 23 36 5 440 major market growth (on a percentage basis)
1970 172 9 23 50 7 515 expected in Asia [14] has not occurred, because
1975 159 18 14 63 7 515 genetically modified organism (GMO) regula-
1980 50 68 5 54 2 430
1985 57 82 2 59 1 460
tions have complicated maize procurement and
1990 75 100 4 75 1 500 low sugar prices have reduced substitution
1997 135 118 5 90 2 560 incentives [15]. Consumption of glucose –
2002 145 520 fructose syrups increased in the United States, on
Glucose – fructose syrups
average, by 19 % annually between 1980 and
1970 18 41 9 1 5 75
1975 127 281 63 5 36 700 1985 and grew much faster than population (4 %
1980 363 1093 236 14 141 2880 annually) between 1990 and 1995. The per capita
1985 424 4204 286 39 211 7180 nutritive sweetener consumption in the United
1990 440 5250 480 40 260 8270
States peaked about 1999; since then, per capita
1997 520 5270 660 45 360 10990
2002 660 5320 12060 consumption of glucose – fructose syrups has
Glucose-containing syrups fallen about 1 % per year [16]. Imports of sugar-
1965 209 36 104 408 159 1155 containing products may explain some of this
1970 222 95 100 440 213 1380 reduction but reasons may also include reduced
1975 313 204 172 417 277 1890
1980 195 385 127 444 240 1840
economic activity and a drop in the consumption
1985 142 356 141 467 274 1940 of baked goods and cereal products in the United
1990 180 365 165 480 275 2125 States [17].
1997 200 370 170 490 350 2955
2002 180 2780
Chromatographic enrichment to > 90 %
fructose syrups has allowed the economical
48 Glucose and Glucose-Containing Syrups Vol. 17

production of crystalline fructose (! Fructose,


Section 2.1) [18]. New drying and encapsulation
technology 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


structure of glucose was elucidated by EMIL
FISCHER. He found that the six carbon atoms of
the glucose molecule are linked in a straight
chain. At first glucose was thought to be an
open polyhydroxy 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
Figure 3. Mutarotation and alkali isomerization of glucose
hydroxy group at C 5. As a result, glucose does
not undergo the specific addition reactions
(e.g., with ammonia or sodium bisulfite) that from one anomeric form to the other through
are typical for aldehydes. the open chain aldehyde form (see Fig. 3).
Glucose predominantly occurs in nature in Chemical structure and conformation have
the form of the D-enantiomer which is therefore been confirmed with the aid of high-field
important commercially. D-Glucose is generally nuclear magnetic resonance spectrometry using
believed to exist in three crystalline forms: super-conducting magnets, advanced pulsars,
and expanded computer capabilities to perform
anhydrous a and b-D-glucose crystals are both
one and two-dimensional Fourier transform
orthorhombic while a-D-glucose monohydrate
experi-ments [24].
crystals are monoclinic (see Fig. 2). However, a
fourth form, thought to be a hydrated form of
b-D-glucose, has been reported [22]. 2.2. Physical Properties

Conformation. In aqueous solution, D- Some important physical properties of crystal-


glucose exists as a mixture of the a and b 4C1 line D-glucose are shown in Table 2. The large
chair forms (approximately 62 % b and 38 % a positive heat of solution of the crystalline
when equilibrated at 31 C [23]) that mutarotate mono-hydrate form imparts a unique cooling
effect to the palate when incorporated into
candy and icing in the crystalline state.

Table 2. Physical properties of D-glucose

a-D-Glucose a-D-Glucose b-D-Glucose


hydrate
Formula C O CH O
½a&D20
H O
6 12 6
!
a C6H12O6 H2!
a 6 12 6 !
a

Optical rotation 112.2 52.7 112.2 52.7 18.7 52.7


Specific heat of þ 59.4 þ105.1 þ 26.0
solution (25 C),
kJ/kg
Figure 2. Crystal forms of glucose [20], [21] A) a – Mono-
hydrate; B) a – Anhydrous; C) b – Anhydrous * Rotation of an a/b equilibrium mixture
¼
52.7 .
Vol. 17 Glucose and Glucose-Containing Syrups 49

Table 3. Fermentable extract values of glucose and glucose-contain-


ing syrups a

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]
a
DE ¼ dextrose equivalents; db ¼ dry basis.

(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
Figure 4. Phase diagram for glucose – water solutions
a) a-Glucose monohydrate and ice; b) Ice and solution;
inhibits oxidative degradation in food; glucose
c) Solubility of glucose in water; before mutarotation to a-
maintains the bright red color of tomato catsup,
,b-equilibrium; d) Anhydrous a-glucose and solution (a-, red berry preserves, and red meats without the
b-equilibrium); e) a-Monohydrate and solution (a-,b- need for artificial antioxidants.
equilibrium); f) a-Glucose (monohydrate and anhy-drous); Glucose is fermented rapidly and completely
g) b-Glucose and solution; h) Unsaturated solution
by yeast and other organisms. The degree of
fermentation possible (or fermentable extract)
of glucose and glucose-bearing syrups is shown
Solubility is an important property of glu- in Table 3.
cose since it is crystallized commercially from
aqueous solution and many of its commercial
uses involve water systems. The solubility of 3. Raw Materials
glucose in water is shown in Figure 4 [25].
Below a temperature of ca. 100 C, the stable, Starch (! Starch) is, for all practical purposes,
crystal-line form of D-glucose is the a-form, the only raw material used for commercial pro-
which crystallizes as a monohydrate below ca. duction of glucose-containing syrups today,
50 C; above ca. 100 C, the b-anhydrous form is although efforts have been made to utilize the
most stable. other natural glucose polymer, cellulose, as
well (! Ethanol, Section 5.4.3.).
All starches are polymers consisting of a-
2.3. Chemical Properties linked anhydroglucopyranose units (Fig. 5 A).
Two types must be distinguished: Amylose (Fig. 5
Above a pH of 6.3, the open aldehyde form of B) is an essentially linear molecule in which the
glucose rearranges to keto-D-fructose (Lobry de anhydroglucopyranose units are linked almost
Bruyn–van Ekenstein rearrangement ! Carbo- exclusively via a-1,4-bonds. Amylopec-tin (see
hydrates: Occurrence, Structures and Fig. 5 C) is a much larger, highly branched
Chemistry, see Fig. 3). molecule (the molecular mass of amy-lopectin is
Glucose is a reducing sugar, i.e., it reacts ca. 1000 times that of amylose [29]); a-1,4
with oxidizing agents such as cupric hydroxide. linkages predominate but there are a significant
Cupric hydroxide oxidizes reducing sugars number of a-1,6-linkages which lead to
more rapidly if the copper is kept in solution by branching. The proportion and structure of these
the formation of a complex salt with tartrate ion fractions in starch granules vary, depending
50 Glucose and Glucose-Containing Syrups Vol. 17

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 a-1,4
bonds
C) Amylopectin. Each ‘‘bead’’ represents an anhydroglucopyranose unit.
D) A branch point is detailed to show an a-1,6 bond

on the botanical source of the starch (Table 4). In sources is higher (ranging from 1000 to 6200).
general, amylose from grain sources has a lower The amylopectin fractions have a much greater
degree of polymerization (DP), ranging from 200 DP, averaging about 2 106 with no major
to 1800, the DP of amylose from root or tuber difference between starch sources.

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 ¼ dry basis
Vol. 17 Glucose and Glucose-Containing Syrups 51

Maize has become the leading source of starch In Thailand, for example, a syrup called
for conversion to sweeteners [34], although starch ‘‘Chinese Maltose’’ is produced from wheat and
from barley, sago, sorghum, wheat, rice, potato, glutinous rice. In Pakistan, broken rice is used to
tapioca, and other starch-bearing grains and roots produce 42 % fructose and enzyme – enzyme
serves as the raw material for the production of glucose syrups having qualities comparable to
glucose-containing syrups around the world. products made from maize starch.
About 70 % of the world production of maize
starch is converted to glucose-containing
sweeteners; nearly 100 % of the glucose-based 4. General Principles of Starch
sweeteners produced in the United States and 84 Hydrolysis
% of the production in Japan are from maize. In
Japan it is required by law that one part potato Hydrolysis of starch occurs when linkages
starch is used for every 12 parts corn starch for between the anhydroglucopyranose units are
fructose syrup production. Although the use of broken catalytically (by using either acid or
wheat starch (as a coproduct of vital gluten enzymatic catalysts in the presence of heat)
production) is increasing in Europe, glucose- with the addition of water. The formation of the
containing sweeteners produced there also monomer (D-glucose) and of dimers having a
originate from maize starch. In Australia, how- 1,4-(maltose) or 1,6-(isomaltose) configuration
ever, all glucose-bearing syrups are produced are shown in Figure 6.
from wheat starch. Mutarotation, (see Section 2.1), isomeriza-
In Asia, factories often use sago, tapioca, or tion reactions (see Section 2.3), and possible
maize (corn) starch for glucose production, repolymerization reactions, coupled with the
depending on the availability and price of each complex chemical structures of amylose and
ingredient. The starch source and purity have a amylopectin (which offer a number of possible
strong influence on manufacturing require- hydrolysis sites), provide the potential for the
ments, but a variety of starches can be used creation of molecules having a nearly infinite
successfully. number of combinations of ketohexose units

Figure 6. Hydrolysis of anhydroglucopyranose polymers


52 Glucose and Glucose-Containing Syrups Vol. 17

(! Carbohydrates: Occurrence, Structures and (detected by blue or purple hue with iodine
Chemistry). staining) leads to difficult separation and must
A simplified flow diagram illustrating the be avoided.
process steps used to manufacture sweeteners Additional impurities are removed by refin-ing
from starch is shown in Figure 7. Starch hydro- with activated carbon, decolorizing resins, or ion-
lysis is catalyzed by both acids and enzymes. exchange resins, either singly or in com-bination,
Irrespective of the catalyst used, all processes before evaporation to final product solids
begin with a water slurry of starch granules. After concentration. Because color-forming bodies are
hydrolysis, insoluble protein, lipid material, and ionic in nature and are efficiently removed by
some of the inorganic components present resins, the total demineralization of syrups, with
initially in the starch are separated by either or without carbon treatment, provides a product
centrifugation or filtration (or both). The pres- with improved color removal and color stability
ence of free starch due to incomplete hydrolysis [83]. And, the removal of

Figure 7. Simplified process flow for the production of sweeteners from starch
* HFS ¼ High-fructose syrup
Vol. 17 Glucose and Glucose-Containing Syrups 53

Table 5. Classification of glucose-containing syrups according to Table 6. Saccharide composition of acid-hydrolyzed glucose syrups
dextrose equivalents (DE)
Dextrose equivalent (DE) of glucose syrup
Degree of hydrolysis Accepted terminology Degree of
polymerization 27 – 30 34 – 36 42 – 43 55
< 20 DE maltodextrins
20 – 38 DE type I syrup DP 1 (glucose) 9 – 10 13 – 14 19 – 20 31
38 – 58 DE type II syrup DP 2 (maltose) 8–9 11 – 12 14 18
58 – 73 DE type III syrup DP 3 (maltotriose) 9 – 10 10 12 12 – 13
DP 4 (maltotetrose) 7–8 8– 9 9 – 10 10
73 DE type IV syrup
DP 5 (maltopentose) 7 8 8 7
DP 6 (maltohexose) 6 6– 7 7 5
ionic material, notably chloride ions, reduces DP 7 (higher sugars) 50 – 54 40 – 42 29 – 31 16 – 17
the corrosives tendencies of syrups allowing
the use of less expensive materials of construc-
tion in process equipment located after ion
exchange.
Glucose-containing syrups are generally When the desired degree of conversion is
categorized by their degree of conversion as achieved, temperature and pressure are reduced
measured by the amount of reducing sugars and the reaction is stopped by addition of a
present. Although it is becoming more common neutralizing agent (usually sodium carbonate),
for customers to specify a range of saccharide raising the pH to 4 – 5.5. Insoluble compounds
distribution to obtain desired functionality, are then removed, and the syrup is refined and
glucose syrups can be divided into groups on evaporated to the desired final concentration.
the basis of their dextrose equivalent (DE) as While acid conversion is a random-action
shown in Table 5. mechanism, it results in remarkably reproducible
Most glucose-bearing syrups are sold in liquid saccharide composition for any given degree of
form usually containing between 70 and 85 % dry hydrolysis. Typical compositions of acid glucose
substance, but they can also be dried to form syrups are shown in Table 6. This reproducible
granular, semicrystalline, or amorphous pro-ducts. composition is actually a limitation of the acid
These ‘‘solid syrups’’ range in degree of process because the manufacturer cannot influ-
conversion from low-DE maltodextrins to highly ence the saccharide distribution for a given degree
converted (> 96 % DE) ‘‘total sugars’’ [84]. of conversion, which is important in some
applications of glucose syrups.
Additionally, acid syrups having a DE value
4.1. Production and Properties of Acid below ca. 30 will tend to cloud upon standing
Glucose Syrups due to precipitation (retrogradation) of the lon-
gest chain linear polymers. Also, although acid
In the acid conversion process, a starch slurry hydrolysis to DE values in the high 80s is
usually having a dry substance content between possible, the extreme conditions required to
30 and 40 wt % is acidified to pH 2 or lower produce DE values greater than ca. 55 promote
and subjected to a combination of time, the formation of excessive amounts of glucose
tempera-ture, and pressure to effect hydrolysis. degradation products (e.g., 5-hydroxymethyl-
Higher temperature, permitted by operation furfural see Section 2.3) which are difficult to
under pressure, reduces the reaction time remove during refining. These color precursors
consider-ably. KIRCHOFF’s conversion at cause the product to yellow eventually. The
atmospheric pressure, for example, lasted 36 h, most common acid glucose product has a DE
early starch converters that were limited to value of about 40 – 45 % because of these
pressures of 35 kPa took 6 h to complete the upper and lower conversion limitations.
reaction. At 415 – 620 kPa and up to 160 C, The limitations at both the low and the high
modern converters accomplish the conversion ends of the conversion spectrum, coupled with
within minutes. Acid conversion can be the inflexible saccharide distribution resulting
accomplished by using either batch or from acid hydrolysis, led manufacturers to
continuous equipment although continuous investigate enzymatic hydrolysis as a means of
conversion is used almost universally today. making improved glucose-containing syrups.
54 Glucose and Glucose-Containing Syrups Vol. 17

4.2. Production and Properties of lized enzyme treatment, the degree of conversion
Acid – Enzyme Glucose Syrups is controlled by the flow rate through a bed of
insoluble enzymes; because the enzymes remain
Coupling a secondary enzymatic hydrolysis to in the converter, their removal from the syrup is
a preliminary acid cleavage allows expansion unnecessary. Refining and evaporation follow as
of the range of DE values both up and down. It in acid glucose syrup manufacture.
also permits control over the saccharide Bacterial a-amylases (E.C. 3.2.1.1) [9000-
distribution by enzyme selection. 90-2] cleave a-1,4-linkages in a random
After acid hydrolysis, the temperature is low- fashion whereas b-amylases (E.C. 3.2.1.2)
ered and the pH is raised to levels compatible [9000-91-3] (and to a lesser degree, fungal a-
with the enzyme to be used; a pH between 4 and amylases) mainly produce maltose, again only
6, and a temperature in the range of 60 – 70 C are cleaving a-1,4-linkages. Glucoamylase (E.C.
usually employed. Additionally, the degree of 3.2.1.3) [9032-08-0], on the other hand, splits
acid hydrolysis is usually (but not always) lower off one glucose molecule at a time from the
when making acid-enzyme syrups (see also ! non-reducing end of the polymer by
Enzymes, 3. Food Application, Section 3.2.). hydrolyzing a-1,4-linkages; glucoamylase also
If the goal is a high glucose content, control has the capability of splitting a-1,6 linkages but
of the acid hydrolysis step to produce a DE of at a much slower rate. Pull-ulanase (E.C.
10 – 20 is important. Higher DE levels result in 3.2.1.41) [9075-68-7] can split a-1,6-linkages,
reduced glucose yield during subsequent enzy- and addition of this enzyme in combination
matic hydrolysis due to the presence of acid- with another enzyme(s) increases the capability
polymerization products that resist enzymatic of tailoring saccharide distributions [30].
conversion; conversely, starch retrogradation At first, enzyme conversion was used to
can occur with a DE less than 10, resulting in extend the degree of conversion upward,
problems during clarification. primar-ily to maximize glucose production for
If maximum glucose content is not the aim, a the manufacture of crystalline glucose as well
higher DE value is usually chosen and the syrup as for the production of sweeter, less viscous
can be clarified immediately after acid hydrolysis glucose-containing syrups. However, it also
or the insoluble substances can be allowed to enabled selective production of either more
remain during enzymatic conversion. maltose or more glucose, depending upon the
If the insoluble compounds are removed, the enzyme chosen. This is illustrated by the
acid hydrolysate can be enzymatically compositional data shown in Table 7.
converted continuously, by using immobilized
enzymes; otherwise, a batch treatment (with
single use of the enzymes) must be employed. 4.3. Production and Properties of
When the desired level of enzymatic conver- Enzyme – Enzyme Glucose Syrups
sion is achieved by batch conversion, residual
enzymes are deactivated with heat or pH adjust- The development of a-amylase from bacterial
ment, or are removed by refining. With immobi- sources capable of withstanding the high

Table 7. Saccharide composition of various acid – enzyme glucose syrups

High maltose High glucose

DE DE 42 – 43 DE 48 – 50 DE 60 – 63 DE 70 DE 95

DP1 (glucose) 6–8% 9 – 10 % 31 – 36 % 43 – 47 % 92 %


DP2 (maltose) 40 – 45 % 50 – 53 % 31 – 36 % 27 – 30 % 4%
DP3 (maltotriose) 12 – 15 % 14 – 15 % 10 – 13 % 5–7% 1%
DP4 (maltotetrose) 3–7% 1–2% (DP4þ ¼ 20 – 23 %) 4–5% 1%
DP5 (maltopentose) 2% 2% 3–4% (DP5þ ¼ 2 %)
DP6 (maltohexose) 2% 2% 2–3%
DP7þ (higher polymers) 26 – 30 % 18 – 20 % 9 – 10 %
DP ¼ Degree of polymerization.
Vol. 17 Glucose and Glucose-Containing Syrups 55

temperature needed to gelatinize starch Table 8. Effect of conversion method on composition of filtered
unrefined highly converted glucose-containing syrup
completely allowed the development of totally
enzymatic processes that further expanded Conversion method
control of saccharide range and distribution. A
total enzymatic conversion process eliminates Acid Acid – enzyme Enzyme – enzyme
the need for preliminary acid hydrolysis. Glucose content, % 86 93 97
Thermostable a-amylases are added to a Ash content, % 1.6 0.4 0.1
starch slurry (containing calcium as an enzyme HMF content, ppm* 3000 80 30
Color (relative) 10 0.3 0.2
stabilizer) that has been adjusted to a pH of 6 –
6.5. A pH lower than 6.3 is preferable to *
HMF ¼ 5-hydroxymethylfurfural.
prevent the formation of maltulose (4–O-a-D-
glucopyr-anosyl-D-fructose) [35]. Maltulose
This higher glucose yield is produced at the
cannot be converted enzymatically to glucose
expense of increased evaporation cost and risk of
and its formation reduces glucose yield.
microbial contamination, and is seldom used
The recent introduction of a novel a-amylase
commercially because chromatographic separa-
capable of liquefying starch at pH 4.5 without the tion technology has become available and allows
need for calcium ion addition has the potential to the increase of the glucose content of syrups to be
reduce chemical and refining costs as well as
> 99 wt % db. Nanofiltration has also been
possibly eliminate the formation of maltulose. used to enrich glucose content [37].
This enzyme’s action pattern reportedly can
Total enzymatic conversion also affects the
increase the production of saccharides with low
characteristics (via saccharide distribution) of
DP (1 – 4) while practically eliminating the higher less highly converted glucose-bearing syrups,
saccharides (DP 8þ). This characteristic allows as shown in Table 9. Syrup viscosity is an
higher solids levels during liquefaction important property that can be affected by
[36]. While presently employed for the shifting saccha-ride distribution.
manufac-ture of ethanol from starch and whole The viscosity is increased mainly by the
grains, the application in the manufacture of longer chain polysaccharides. Thus, at a con-
starch sugars holds interest. stant DE value, solids content, and temperature,
The slurry is heated, usually by direct steam an acid-hydrolyzed syrup would have the high-
injection, to ca. 103 – 107 C and held for 5 – 10 est viscosity, an acid – enzyme syrup would be
min to liquefy the starch completely. A sub- intermediate, and an enzyme – enzyme syrup
sequent holding period of 1 – 2 h at about 95 C would have the lowest viscosity. Viscosity
allows continued enzymatic activity to raise the affects the handling and storage temperature as
DE to a value between 10 and 15. The tempera- well as the application properties. Many desir-
ture and pH are then adjusted to levels compati- able results occur from lowering the viscosity,
ble with the enzyme used for the secondary including improved flavor release in sweets,
conversion. From this point, the process is lowering of boiling temperature in candy man-
similar to the acid – enzyme process. ufacture, faster operation of candy production
On the high end of the glucose conversion lines, and better ‘‘set’’ in jellies and jams.
scale, a totally enzymatic conversion greatly
increases the yield of glucose while decreasing Table 9. Saccharide distribution of 42DE syrups produced by differ-
the refining requirements. The composition of ent conversion methods
highly converted syrups produced by acid, acid
– enzyme, and totally enzymatic hydrolysis Conversion method
Degree of
with respect to glucose concentration and polymerization Acid Acid – enzyme Enzyme – enzyme
impurity content is shown in Table 8.
DP 1 19 6 2.5
Maximum glucose content during glucoamy- DP 2 14 45 56.0
lase saccharification is also determined by solids DP 3 12 12 16.0
content in the slurry; at 30 wt %, a glucose level DP 4 10 3 0.7
of 96 wt % db is usually achieved. Decreasing the DP 5 8 2 0.4
solids content to 10 – 12 wt % allows glu-cose DP 6 7 2 0.7

levels of 98 – 99 wt % db to be reached. DP 7þ 30 30 23.7


56 Glucose and Glucose-Containing Syrups Vol. 17

Enzymatic conversion also allows the pro- ous solidification process that employs spray
duction of syrups with reduced glucose content. drying of a partially crystallized, refined hydro-
In the presence of protein, glucose undergoes lysate [38], [39].
non-enzymatic browning due to the Maillard However, with the exception of a relatively
reaction more readily than polymers of glucose. small amount of spray-dried hydrolysate
Syrups with higher concentrations of glucose products (a monohydrate product with the trade
polymers are more color stable. name Cantab produced by Penford Products
Products Co., United States and an anhydrous
product manufactured by Cargill, United
5. Production of Solid Glucose Kingdom/ United States), total sugars have not
been the large market successes in the West
Whereas most glucose is sold as glucose- that they have in the Orient; in Europe and the
containing syrups, a portion is sold as granular Americas, pure glucose crystals (in either the
free-flowing solids. In this form it can be incor- monohydrate or the anhydrous form) are the
porated into dry mix products and shipped more universally accepted product.
without the added cost of transporting water.
Bagged product accommodates smaller-scale
users. Solid products include total sugars and 5.2. Production of Pure Crystalline
pure crystalline forms of glucose (dextrose). Products
Total sugars are solidified hydrolysates that can
either be in glassy (amorphous) or crystalline Initially, crystalline glucose was produced from
states. Pure glucose crystals are grown from acid-converted starch hydrolysates. Because of
aqueous solution to form a slurry of pure degradation products formed during
crystals in mother liquor (massecuite), the crys- conversion, the maximum glucose content
tals are separated from the mother liquor by achievable in the hydrolysate was limited to
centrifugation and dried in hot air dryers. about 88 % db. By 1938, enzymatic conversion
processes were being developed that provided
much purer sources from which crystalline
5.1. Production of Total Sugars glucose could be manufactured.
Either continuous or batch crystallization
When the entire starch hydrolysate is solidified, it can be used to produce the desired crystals. In
is called a total sugar. A variety of processes have con-tinuous crystallization, supply liquor is
been developed to produce total sugars [84]. Dry either mixed with recycled seed crystals or new
maltodextrins have a DE of less than 20 while crystals are formed by spontaneous nucleation.
corn syrup solids have higher DE values, com- In batch crystallization, a portion (usually 15 –
monly between 24 and 48. Highly converted total 30 %) of the finished batch is retained in the
sugars usually contain between 95 and 99 % db crystallizer and mixed with the supply liquor.
glucose although processes have been patented Supersaturation to promote crystal growth
for the production of fructose-bearing total sugars can be achieved by either cooling or
and solid starch sugars that incorporate other evaporation [40], [41]. When continuous
ingredients such as intense sweeteners. crystallization is employed for the production
About 40 % of the crystalline glucose sold of monohydrate dextrose crystals that form
in Japan is a solidified hydrolysate (total sugar below 50 C, great care must be taken to prevent
form) of monohydrate glucose distantly related microorganisms, primarily yeast, from acting
to the cast product produced early this century on the glucose solution. Yeast fermentation is
(but of much higher purity due to enzymatic only a problem at the lower temperature and
starch hydrolysis, modern refining methods, solids levels, that occur at high crystal content
and evaporation under high vacuum). at the final crys-tallization conditions.
More than half of the crystalline glucose sold When producing glucose monohydrate, batch
in Korea is also a monohydrate total sugar that is crystallization has the advantage that the operat-
used as a carrier in many dry foods. These total ing conditions at the beginning of the cycle
sugars are produced by using a modern, continu- (highest temperatures and solids content) are
Vol. 17 Glucose and Glucose-Containing Syrups 57

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 product to
be mixed with supply liquor for the next batch, a
more efficient process for the production 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 hostile to yeast, and
then supplying this material to a batch crystal-
lizer to produce a high-crystal-content masse- Figure 8. Batch monohydrate glucose crystallizer A) Cut-
cuite suitable for centrifuging, the full operating away view showing internals a) Motor and Speed reducer
volume of the batch crystallizer is used for which drives coil; b) Cooling water connections; c)
Rotating coil – agitator; d) External vessel shell
production; the batch crystallizer is completely
B) External side view a) Supply liquor inlet; b) Inspection
emptied at the end of the crystallization cycle, and hatch; c) Bearing; d) Cooling water connections; e) Support
the processing time devoted to seed mixing is saddle; f) Massecuite discharge valve
eliminated.
Since anhydrous glucose crystals form above during which about 60 % of the glucose is crys-
50 C, yeast fermentation is not an issue and tallized in the a-monohydrate form, yielding a
either batch or continuous crystallization can be viscous magma of crystals and mother liquor.
used. Exact values of the solids concentration, the
initial and final temperatures and the rate of
Production of Glucose Monohydrate Crys- cooling depend on the glucose content of the
tals. The a-D-glucose monohydrate crystals, crystallizer supply [44–46].
usually produced by batch crystallization, have The resulting magma is routed to perforated
the largest share of the world market. Starting screen centrifuges (usually batch machines) to
material for the manufacture of glucose crystals separate most of the mother liquor from the
is a syrup with a glucose content of 95 – 96 wt crystals; most of the remaining mother liquor is
% db produced by enzymatic hydrolysis of then removed by washing the crystals with a
starch to the highest practical degree. This spray of water.
syrup is produced and refined by using the The crystals are spun as dry as possible (about
process described previously for the production 14 wt % moisture content) and then transferred
of enzyme – enzyme glucose syrups. to continuous rotary dryers (! Drying of Solid
In a typical batch crystallization process, the Materials) where they are dried in a stream of
syrup is evaporated to a solids content of 74 – 79 warm, filtered air to 8.5 – 9.0 wt % moisture
wt %. Higher solids content results in in-creased content, slightly below the theoretical moisture
crystallizer productivity [43]. The supply is cooled content of the monohydrate (9.08 wt %).
to about 46 – 50 C, and mixed with seed crystals Because crystallization of glucose monohy-
(left behind from the previous batch) in drate occurs satisfactorily despite the presence of
crystallizers (see Fig. 8). As mentioned large quantities of impurities [4], [47], the mother
previously, an alternative process having greater liquor can be reconcentrated and a second crop of
productivity would utilize continuous crystalli- crystals can be recovered. The presence of
zation to produce a lean massecuite that would be impurities alters the crystal size and shape; purer
supplied to the batch crystallizer, thus allowing liquors produce longer, narrower crystals than
complete emptying of the batch unit at the end of those produced from less pure solutions [48].
the cycle. Alternatively, continuous crystalliza- Otherwise, a portion of the mother liquor can
tion could be used entirely. be recycled and combined with the incoming
The resulting mixture is cooled slowly, hydrolysate as supply to a single crystallization
usually by indirect heat transfer to a final tem- step. Either process increases the yield of glucose
perature between 20 and 40 C over 2 – 5 d crystals from a given amount of hydrolysate.
58 Glucose and Glucose-Containing Syrups Vol. 17

Recovery of as much as 87.5 % of the glucose Sweetening Power. Sweetening power


from the incoming hydrolysate as monohydrate cannot be measured quantitatively in absolute
crystals has been reported [49]. By terms but can be determined subjectively by
reconverting the mother liquor, yields using trained taste panels. Many factors includ-
approaching 100 % have been reported [85]. ing stereochemical configuration influence the
perception of sweetness: a-glucose is definitely
Production of Anhydrous Crystalline Glu- sweeter than the b-form [51]. Stereochemistry
cose. Anhydrous crystalline glucose is pro-duced can explain the wide variation in reported
in evaporative crystallizers operated in either a sweetness of fructose, whose crystalline form
batch or a continuous mode. Anhydrous a-D- b-D-fructopyranose undergoes rapid tautomer-
glucose is usually produced in batch vacuum pan ization in solution to five forms: a and b-D-
evaporative crystallizers operated at 60 – fructopyranose as well as a and b-D-fructofur-
65 C. The crystallization cycles are much shorter anose and open chained keto-D-fructose. Thus,
than those needed for monohydrate production, although crystalline fructose is reportedly 1.8
usually only 6 – 8 h [4]. The crystals are separa- times as sweet as sucrose, solutions of fructose
ted from the mother liquor, washed, and dried in a are much less sweet than crystalline fructose
manner similar to monohydrate crystals, but the because of the tautomeric distribution in water
final product moisture is less than 0.1 wt %. [52].
Production of anhydrous glucose crystals is Concentration [51], temperature, and pH
more demanding than that of their monohydrate [53] affect the perception of sweetness too. To
relatives and they can only be successfully crys- elimi-nate the possibility of enzymatic
tallized from relatively pure solutions [4]. The hydrolysis in the taster’s mouth, rapid and
purest grades (U.S.P.) are produced from very consistent evaluation procedures are required,
pure glucose syrups made by dissolving mono- especially when tasting low-DE syrups.
hydrate glucose crystals in water. In general terms, however, as the glucose
Anhydrous b-D-glucose can be produced by content of glucose-containing syrups increases,
operating the crystallization step slightly above sweetness increases; as glucose is isomerized to
100 C [4]. Another commercial method of pre- fructose, sweetness increases further. The
paring a crystalline glucose total sugar rich in the sweet-ness of glucose-containing syrups,
b-anomer consists of spraying a hot, concentrat- relative to sucrose, in solutions of about 10 wt
ed glucose syrup onto a moving bed of previously % solids concentration is shown in Figure 9.
made product at high temperatures (85 – Most glucose–fructose syrups are usually
105 C) in a rotary dryer to yield a granular, pro-duced from enzymatically converted high
pearl-shaped crystal [50]. glu-cose (95 – 96 % db) hydrolysates which are
The b-anhydrous glucose is much more solu- the fructose–glucose syrups shown in Figure 9.
ble than the a-form (72 wt % vs. 30 wt % at However, lower DE syrups that have been
25 C, the solubility of the equilibrium a-b- isom-erized slightly to 10 wt % fructose
mixture is 51 wt % at 25 C). content to increase sweetness are sold in the
European Union. Syrups isomerized to this low
level do not violate fructose production quotas
6. Glucose – Fructose Syrups that have been established to protect domestic
sucrose production.
6.1. Properties
Chemical Properties. Fructose reacts with
Isomerization of glucose to fructose significantly amino groups (Maillard reaction) much more
increases the sweetness of starch-based sweet- readily than glucose does (! Fructose) [62].
eners. This single property propelled the market Therefore, glucose – fructose syrups must be
share of starch sweeteners from 20 to over 50 % refined to a greater degree and are inherently
in the United States. More than half of the starch- less stable. Fortunately the higher water solu-
based sweeteners sold in Japan and about two- bility of fructose (! Fructose) allows lower
thirds of those sold in the United States are 42 and storage temperatures without crystallization
55 % fructose syrups. (see Chap. 9).
Vol. 17 Glucose and Glucose-Containing Syrups 59

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]; þ [58]; ~ [59]; !
[60]; ¤ [61];

6.2. Production Immediately after isomerization, the pH is


lowered to 4 – 5, the syrup is refined and
The clarified, refined, and ion-exchanged high- evapo-rated to the final concentration.
glucose-content syrup is evaporated to a 40 –
50 wt % solids level. Magnesium(II) ions Chromatographic Enrichment. Although 42
(usually as MgSO4) are added as a cofactor to % db fructose syrups are nearly as sweet as
activate and stabilize the isomerase enzyme, as sucrose, the fructose content had to be
well as to overcome the inhibitory effect of increased to 55 % db to provide the exact
residual calcium not removed by ion exchange. sweetness match demanded by the soft-drink
This feedstock is then passed through reactors market. This is accomplished by employing
containing immobilized glucose isomerase (E.C. chromatographic separation techniques to
5.3.1.18). Process conditions vary depend-ing separate 42 % fructose syrups into fructose-
upon the supplier of the enzyme but most systems enriched and glucose-enriched streams.
operate at 55 – 65 C and with pH of 7.5 – 8.5. The Separation is accomplished by passing the 42
flow rate is adjusted to yield a product having a % fructose syrup through an adsorbent resin
minimum of 42 % of the dry substance converted containing calcium ions. Fructose is bound to the
to fructose. adsorbent to a greater extent than glucose (and
Enzymatic activity decreases during the polymers of glucose). Elution with water pro-
effective life of the reactors due to thermal duces a discharge stream initially rich in the
inactivation and the presence of trace impurities in loosely bound glucose and glucose polymer
the feed liquor. Fructose content is maintained at fraction, followed by a fraction rich in the more
the desired 42 % level by reducing the flow rate tightly bound fructose. A continuous (simulated
through the columns. The effective life of a moving bed) process is used commercially, in
reactor is several months; during this period, the which 42 % fructose supply liquor and elution
nominal retention time in the reactor may in- water enter the columns at different points, while
crease typically from 0.5 to as much as 4 h. glucose-rich and fructose-rich product streams
60 Glucose and Glucose-Containing Syrups Vol. 17

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 stream
containing 80 – 95 % db fructose is the primary
product (the composition depends on the
equipment and operating conditions). This fruc-
tose-rich stream is blended with 42 % fructose
syrup to produce a 55 % fructose syrup that is
refined and evaporated to the final concentration.
The fructose-rich stream can also be refined
and evaporated to about 80 wt % solids for
customers requiring a very high fructose-
content product. At the highest fructose levels,
it can supply a crystallization process to
produce fruc-tose crystals.
In 1987 more than 80 commercial factories
on almost every continent were reported to Figure 10. Growth of glucose – fructose syrup production,
produce more than 6.6 106 t (dry basis) per year 1968 – 2005
of glucose–fructose syrups [65]. Worldwide
pro-duction increased to 10.1 106 t (dry basis)
per year in 1995 and is estimated to have grown been described [67]. The pH of extracts is raised
to nearly 12.5 106 t (dry basis) in 2002 before to > 11 using lime, to precipitate impurities.
dropping to 11.8 106 t (dry basis) per year in Under these conditions, inulin is not precipitated
2005 [14]. The phenomenal growth of glucose by high levels of calcium (as is fructose) and can
– fructose syrup (called high fructose corn be recovered by filtration [68].
syrup or HFCS in the United States) production The lack of commercial interest in high-fruc-
is shown in Figure 10. tose syrup production from inulin is probably due
to the high quality of fructose syrups produced by
isomerization of glucose followed by chro-
6.3. High-Fructose Syrups from Inulin matographic separation, and to lack of the large
crop production industry needed to produce inu-
Inulin is a naturally occurring polymer of fruc- lin. While the Jerusalem artichoke is reported to
tose which replaces starch as the food reserve produce tuber yields as high as 100t/ha [86],
in many plants of the family Compositae (e.g., present commercial sources of inulin are primar-
Jerusalem artichoke, chicory, salsify, cardoon ily obtained from chicory [87]. While some
elecampane, burdock, dahlia, and ti plants). fructose is being produced, much of the inulin is
The mature inulin molecule has an Mr of partially enzymatically hydrolyzed to make a
3000 – 5000 and consists of 17 – 30 anhydro- range of nondigestible oligofructose ingredients
fructose units and a terminal glucose unit (see that are finding use as fat mimetics. Only the
Fig. 11). The chain length varies during the European Union is a substantial producer of
growing season, and consequently, the glucose fructose-containing inulin syrup that originally
– fructose ratio is not constant [66]. was not limited by production controls as was
A process for the production of high-purity glucose-derived fructose syrups. Inulin syrups
fructose syrup from inulin-containing roots has have now been brought under control by the EU.
Vol. 17 Glucose and Glucose-Containing Syrups 61

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
absorbed 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
distinguish (visually) between syrups and water.

8. Legal Aspects

The legal aspects of glucose-containing pro-


ducts 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 Pharmacopeia. In the United States,
glucose syrups and monohydrate and
anhydrous crystalline glucose are considered
Figure 11. Part of an inulin chain
standardized foods by the U.S. Food and Drug
Administra-tion, while fructose syrups derived
from glucose are considered as GRAS
(generally regarded as safe) with specifications
defined by the Food Chemicals Codex of the
National Academy of Sciences.
7. Analysis
Solid Concentration. The Codex Alimen-
Solids concentration of glucose-containing syrups tarius Commission recommends that the solids
is usually measured by refractive index or density. content of glucose-containing syrups be no less
This measurement can be related to dry substance than 70 wt %. The U.S. Code of Federal
or the more traditional Baume or specific gravity Regulations (CFR) specifies that anhydrous
values by using established mathematical models crystalline glucose contain no less than 98 wt %
and conversion factors that compensate for syrup dry substance (in practice, the commercial
composition. Glucose-containing syrups are sold prod-uct usually contains < 0.1 wt % water) and
at concentrations usu-ally varying between 75 and that monohydrate crystalline glucose contain no
85 wt % solids. Glucose–fructose syrups are less than 90 wt % dry substance (in commercial
usually produced at 71 – 75 wt % solids for the 42 practice, dry substance ranges between 91 and
% fructose syrup and 75 – 77 wt % solids for the 92 wt %).
55 % fructose product. The moisture content of
dry products (crystalline glucose and solid glucose Carbohydrate Composition. The Codex
syrups) is usually measured by weight loss under Alimentarius recommends that glucose syrups
vacuum drying or by Karl Fischer titration. have a DE value not lower than 20 (below this
level they are defined as maltodextrins). The
The carbohydrate composition of glucose and CFR requires that crystalline glucose have a DE
glucose–fructose syrups is almost always mea- value no less than 99.5 [66].
sured by high performance liquid chromatogra-
phy (HPLC). The carbohydrate composition can Impurity Content. Ash content limits of 1 wt
be related to the traditional dextrose equivalent % for syrups (Codex Alimentarius) and 0.25 wt
(DE) by calculation [69]. However, direct % for food-grade crystalline glucose
62 Glucose and Glucose-Containing Syrups Vol. 17

Table 10. Storage conditions of glucose-containing syrups


(CFR) are met easily by modern ion-exchange
refining. The U.S. Pharmacopeia places much Solids content,
stricter specifications (including specific rota- Syrup type wt % Temperature, C Limiting condition
tion, acidity, residue after ignition, and content
42 DE 80 38 viscosity
of chloride, sulfate, arsenic or other heavy 83 49 viscosity
metals, and other components) on pharmaceuti- 60 DE 82 32 viscosity
cal-grade glucose [72]. 84 41 viscosity
95 DE 71 49 crystallization
42 HFCS 71 32 crystallization
55 HFCS 77 27 crystallization
9. Storage and Transportation 90 HFCS 80 16 crystallization
Liquid glucose 71 52 crystallization
(99.5 DE)
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
reduce the viscosity of low-DE syrups below temperatures of solid products should be lower
15.0 Pa s (to allow handling with lobe or vane than 40 C and rapid temperature changes
pumps) or to prevent crystallization of glucose should be avoided to minimize product caking.
in higher DE syrups. Suggested temperatures Crystalline glucose is shipped in vapor-
for various syrups are shown in Table 10. resistant bags usually containing 50 or 100
Shipping containers for syrups range in size pounds (or the approximate metric equivalent
from 200 L drums to jumbo railcars holding sizes of 20, 25, and 40 kg) and in bulk trucks
90 t. Trucks carrying 25 t are also used. Alter- and railcars (jumbo railcars can hold as much
natives to drums include 1000 L disposable as 82 t). Reusable containers holding about 1 t
containers consisting of reinforced corrugated of crystalline material are used for customers
board outer containers holding a heavy-duty who do not require bulk delivery and who do
plastic bag. not want the bother and expense of bag opening
Bags for storage of crystalline glucose and and disposal.
solid syrups must be protected against atmo-
spheric moisture pickup by incorporation of a
vapor barrier in the bag construction. Storage 10. Uses

Glucose-containing syrups and glucose are


used in a variety of food and nonfood applica-
tions. The manufacturing flexibility provided
by enzymatic conversion techniques, coupled
with modern refining and concentrating tech-
nology, provides a wide range of properties
useful to the food formulator. Table 1 illus-
trates 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 applications can also be seen
from this table. The rapid and complete
fermen-tation 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,
Figure 12. Glucose-containing syrup color as a function of acetic, etc.), enzymes, amino acids, vitamin C,
time and temperature a) 54 C; b) 49 C; c) 38 C; d) 27 C and a variety of antibiotics.
Vol. 17 Glucose and Glucose-Containing Syrups 63

The largest nonfood use of unrefined two products on the growth of the corn wet
glucose-containing syrups is as a carbohydrate milling industry in the United States is shown
source for the production of fuel-grade ethanol in Figure 13. In 2004, corn (maize)
(! Ethanol, Section 5.1.2.). In 1986, the annual consumption for ethanol production amounted
production capability in the United States was to more than half of that consumed by all food
reported to be ca. 2.7 109 L [73] and a 1988 and industrial uses in the United States. While
article indicated a capacity of 3.9 10 9 L annu- the food and industrial use of maize in the
ally [74]. Annual U.S. production capacity in United States has grown substantially since the
2006 was reported as 1.68 1010 L [75] 1970s, farm production has more than kept up.
In other applications, the dehydration of The price of maize during this period has
glucose to 5-hydroxymethylfurfural allows the trended downward (see Fig. 14).
incorporation of glucose-containing syrups into But the real cost of maize to starch-based
phenolic and urea – formaldehyde-based plas- sweetener manufacturers is the cost of maize
tics [76]. Heating glucose and methanol in the (corn) minus the income from the sale of
presence of anhydrous hydrogen chloride yields coproducts of the wet milling process (corn
a-methyl-D-glucoside which is used for insulat- gluten feed, corn gluten meal, and corn oil), i.e.,
ing foams. Catalytic hydrogenation of glucose the net corn cost. Year-to-year, net corn cost
yields sorbitol. has followed corn price in the USA since the
Glucose-bearing syrups are also added to 1970s but the trendlines for corn and net corn
adhesives to improve stability and flow control, cost are converging, indicating an average
used as humectant in wallboard and tobacco reduction in coproduct credit of 37 cents per
manufacture, added to tiles and bricks to bushel over the past 30 years (see Fig. 14.). The
prevent cracking during manufacture, used to rapid growth in starch use in non-sweetener
retard setting in concrete, are applied in resin applications and the impact on raw material
and dye manufacture and leather tanning to cost and the price of glucose-bearing products
name but a few of their nonfood uses. has been analyzed [77], [78]. To date, it appears
that agricultural productivity increases have
more than kept up with expanding food and
11. Economic Aspects industrial use of maize in the United States,
keeping maize cost stable. For wet millers in
The economics of starch-based sweeteners are the USA, increased volumes of coproduct have
related to the economics of sucrose (cane and beet negatively impacted their prices, primarily for
sugar) except for uses in which production costs corn oil and corn gluten feed. Since fuel ethanol
and unique functionality allow higher prices (such production is expected to nearly double by
as high-purity crystalline glucose for intravenous 2012, net corn cost must be watched.
injection) or significant compe-tition causes price
reduction (such as glucose syrups in the United
States). In countries where no protective tariff 12. Physiological Properties and
exists and sucrose is sold essentially at world Toxicology of Glucose
prices, the domestic con-sumption volume of
starch-based sweeteners depends on sucrose Glucose is absorbed into the bloodstream and
pricing. For non tariff nations, consumption and used by the body (via the glycolytic cycle) for
pricing figures can vary significantly from year to energy production or converted into other
year. The produc-tion and pricing of starch-based metabolic intermediates required for growth or
sweeteners around the world are shown in Table maintenance of body tissues. By polymerization
11. into glycogen (a highly branched macromole-
Raw material (starch) pricing is also an cule referred to as body starch), it is also stored
important factor. Competition of markets for in the liver for future use.
starch-based products, primarily used for the Glucose (and other sugars) acts as a dietary
production of high-fructose syrups and fermen- chelating agent under certain conditions, bind-
tation to fuel-grade ethanol has become impor- ing iron and several other di- and trivalent
tant in recent years. The impact of these metals [79]. Simultaneous ingestion of glucose
64 Glucose and Glucose-Containing Syrups Vol. 17

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.)

Crystalline glucose Fructose-glu-


cose syrup

Country Glucose syrups Maltose syrups Monohydrate Anhydrous Total sugar 42 % 55 %

United States
Production 3200 645 25 68 2300 5000
Price, US$/kg d.s. 0.30 0.62 1.25 0.88 0.41 0.45
Europe (EU 15)
Production 2200ab 320a,b 45 330a,b
Price, US$/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 35dd 39dd 44dd 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
90þ% 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 ¼ 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.

and a calcium supplement is reported to boost beginning a high-glucose, lipid-free diet,


the body’s uptake of that mineral by 25 % [80]. whereas single doses of glucose syrup may be
Blood serum cholesterol and phospholipid responsible for improved intellectual perfor-
levels are reportedly lowered within days of mance [81].
Vol. 17 Glucose and Glucose-Containing Syrups 65

8 R. O. Marshall, E. R. Kooi, Science 125 (1957) 468 –


469.
9 CPC International, US 2 950 228, 1960 (R. O. Marshall).
10 J. P. Casey, Starke€ 29 (1977) no. 6, 196 – 204.
11 1965 – 1980 individual industry data reproduced with
permission from: Cereal Foods World 31 (1986) no. 12,
859 and updated with 1985, 1990 1997 and 2002
industry data estimates. Total volumes from USDA
ERS data.
12 United States Dept. of Agriculture (USDA) Sugar and
Sweetener Situation and Outlook Report SSRV 12 N 1,
Mar., 1987.
13 ‘‘Annual Review of the World HFCS Industry’’ in
Figure 13. Growth of corn wet miller’s shipments in the
United States 1929-2005, comprising starch, refinery pro- Sweet-ener Analysis November, 2005, p. 2, LMC
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14 S. Vuilleumier: Int Sugar Jnl. 98 (1996) no. 1173, 467–
478.
15 J. Cropley: ‘‘The Global Market Outlook for Corn
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16 USDA-ERS: Sugar and Sweetener Situation and
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17 S. Haley: ‘‘Measuring the Effect of Imports of Sugar-
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18 P. A. Meyer, Milling & Baking News 65 (1986, Aug.
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19 ‘‘Dry HFCS: Problem Solved, ’’ Food Eng. 59 (1987)
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Figure 14. Average annual corn and net corn price 1 bushel 20 W. B. Newkirk, Ind. Eng. Chem. (1924, Nov.) 1173.
corn ¼ 25.4 kg 21 G. R. Dean, Anal. Chem. 45 (1973, Dec.) no. 14, 2441.

22 G. R. Dean, Carbohydr. Res. 34 (1974) 315 – 322.


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26 J. C. Speck, Adv. Carbohydr. Chem. 13 (1958) 63 – 103.
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59 R. Whymper, Manuf. Confect. 35 (1955) no. 6, 15, 16, Technology, 3rd ed., Academic Press, London 2009.
19, 20, 22. A. C. Bertolini (ed.): Starches, CRC Press, Boca Raton, FL
60 N. Deerr: Int. Sugar J. 24 (1922) 481. 2010.
61 Kirk-Othmer, 3rd ed., 22, p. 508. S. W. Cui (ed.): Food Carbohydrates - Chemistry, Physical
62 L. C. Maillard, Compt. Rend. 154 (1912) 66. Properties, and Applications, CRC Press, Boca Raton,
63 H. W. Keller et al., Starch/Starke€ 33 (1981) no. 2, 55 – 57. FL 2005.
64 J. R. Teague et al., Sugar/Azucar 78 (1983) no. 8, 18 – 23. P. Hull: Glucose Syrups - Technology and Applications,
65 M. Ruffolo: ‘‘Starch and Chemical Sweeteners in the Wiley-Blackwell, Ames, IA 2010.
Changing Sweetener World’’ 3rd Conference of World R. V. Stick, S. J. Williams: Carbohydrates, 2nd ed.,
Sugar Farmers – World Association of Beet and Cane Elsevier, Amsterdam 2009.
Growers, Gold Coast, Australia, July 21, 1987. K. J. Yarema (ed.): Handbook of Carbohydrate
66 J. S. Bacon et al., Biochem. J. 51 (1952) 208. Engineering, CRC Press, Boca Raton, FL 2005.

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