Professional Documents
Culture Documents
FRED W. SCHENCK, Consultant (retired), Sun City, Arizona 85373–1113, United States
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
2. Properties of Glucose
2.1. Structure
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.
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.
* 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
(! 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
DE DE 42 – 43 DE 48 – 50 DE 60 – 63 DE 70 DE 95
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
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
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];
8. Legal Aspects
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.)
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.
36 J. M. Segraves, W. G. Allen, J. Harris, K. L. Pratt: ‘‘Valley 67 M. Kierstan, Process Biochem. 15 (1980) no. 4, 4.
‘‘Ultra-Thin’’ – A novel alpha-amylase for true pH 4.5 68 M. Kierstan, Biotechnol. Bioeng. 20 (1978) 447.
liquefaction’’, Int. Sugar J. 107 (2005) no. 1283, 616–621. 69 D. L. Kiser et al. in G. Charalambous (ed.): Symposium
37 Archer Daniels Midland Company, 5 869 297, 1999 (T. on the Analysis of Foods and Beverages by HPLC,
P. Binder, D. K. Hadden, L. J. Sievers). Academic Press, New York 1979, pp. 363 – 378.
38 Y. Komai, Starke€ 17 (1965) no. 11, 346 – 350. 70 Approved Methods of the American Association of Cereal
39 Nippon Shiryo Kogyo Co., Ltd., US 3 540 927, 1970 Chemists (AACC), 8th ed., AACC, St. Paul, Minn., 1983.
(N. Masahiro, T. Furukawa, H. Masada). 71 Code of Federal Regulations effective April 1, 1987
40 Corn Products Company, US 3 257 665, 1966 (L. R. Title 21 – Part 168 – Section 168.111.
Idaszak). 72 U.S.P., 21st ed., 300.
41 Struthers Scientific and International Corporation, US 3 73 A. S. Greditor: Research Report, CPC International,
506 486, 1970 (N. Geniaris). Drexel Burnham Lambert, New York Nov. 10 1986 13.
42 CPC International, US 4 357 172, 1982 (L. W. Edwards). 74 J. G. Joyce, Investor News 10 (1988) no. 3, 1, 4.
43 A. F. M. Mahbubar Rahman, F. W. Schenck: ‘‘Supply 75 Renewable Fuels Association, From Niche to Nation:
solids level and monohydrate dextrose productivity’’, Ethanol Industry Outlook 2006 available at http://www.
Int. Sugar J. 101 (1999) no. 1207, 379, 380. ethanolrfa.org.
44 Corn Products Refining Co., US 1 508 569, 1924 (W. 76 H. Koch, J. Pein, Polym. Bull. 13 (1985) 525 – 532.
B. Newkirk). 77 F. W. Schenck: ‘‘The impact of growth on the US corn
45 Corn Products Refining Co., US 1 890 913, 1932 (W. wet milling industry’’, Int. Sugar J. 101 (1999) no.
B. Newkirk). 1210, 510– 516.
46 Corn Products Refining Co., US 2 152 874, 1939 (C. J. 78 F. W. Schenck: ‘‘Factors influencing the price of head
Copland). products of the corn wet milling industry’’, Int. Sugar J.
47 P. Elankovan et al, AIChE J. 33 (1987, Nov.) no. 11, 1844. 103 (2001) no. 1234, 462–466.
48 [4] pp. 133, 134. 79 P. Saltman: ‘‘Role of Simple Carbohydrates in Metal
49 R. V. MacAllister in R. S. Tipson, D. Horton (eds.): Absorption,’’ Proc. Corn Refiners Association
Advances in Carbohydrate Chemistry and Biochemistry, Scientific Conference, 1988.
vol. 36, Academic Press, New York 1979, p. 41. 80 Insight 4 (1988) no. 9, 52.
50 Corn Products Refining Co., US 2 369 231, 1945 (A. T. 81 G. G. Birch, M. W. Kearsley, Starke€ 29 (1977) no. 10,
Harding). 348 – 352.
51 C. Nieman, Manuf. Confect. XL (1960) no. 8, 19 – 24, 82 W. S. Spector (ed.): Handbook of Toxicology, vol. I,
43 – 46. Saunders, Philadelphia – London 1956, pp. 150 – 151.
52 S. A. Watson, P. E. Ramstad (eds.): Corn: Chemistry 83 F. W. Schenck, R. E. Hebeda: Starch Hydolysis
and Technology, Am. Assoc. of Cereal Chem., St Paul, Products, VCH Publ., 1992, p. 288.
Minn. 1987, p. 523. 84 F. W. Schenck, Starch/St€arke 48 (1996) no. 5, 188 – 190.
53 L. Hyvonen, et al., Lebensm.-Wiss. Technol. 11 (1978) 85 A. F. M. Mahbubar Rahman, F. W. Schenck, ‘‘Improving
no. 1, 11 – 14. monohydrate dextrose economics with enzymatic recon-
54 M. W. Kearsley et al., Lebensm.-Wiss. Technol 11 version’’, Int. Sugar J. 100 (1998) no. 1197, 457–461.
(1978) no. 1, 23 – 25. 86 M. Parameswaran, Food Australia 46 (1994) no. 10,
55 L. M. Hanover in G. Charlambous, G. Inglett (eds.): 473 – 475.
Chemistry of Foods and Beverages: Recent Develop-ments, 87 P. Coussement, Food Ingredients and Analysis Interna-
Academic Press, New York 1982, pp. 211 – 233.. tional 18 (1996) no. 5, 25 – 27.
56 A. Rapaille et al., Bios, 8 (1977) no. 10, 19 – 22.
57 S. Yamaguchi et al., Agric. Biol. Chem. 34 (1970) no.
2, 181 – 186. Further Reading
58 A. C. Dahlberg et al., New York State Ag. Exp. Station
Bulletin, No. 258, Apr., 1941. J. N. BeMiller, R. L. Whistler (eds.): Starch - Chemistry and
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.