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Hammond Et Al., - Soybean Oil, - Chapter in Bailey's Industrial Oil and Fat Products, 2005 PDF
Hammond Et Al., - Soybean Oil, - Chapter in Bailey's Industrial Oil and Fat Products, 2005 PDF
Soybean Oil
Earl G. Hammond, Lawrence A. Johnson, Caiping Su,
Tong Wang, and Pamela J. White
Iowa State University
Ames, Iowa
1. INTRODUCTION
The amounts of soybeans and total vegetable oil crops have been rising for a
number of years. World production of soybeans in 2003 was estimated to be
184.49 million MT out of 317.89 million MT total for vegetable oil crops, making
soybeans the world’s largest oilseed crop, rivaled only by palm oil (1). The 2003
crop of soybeans was expected to yield 29.85 million MT of soybean oil out of a
total of 91.79 million MT of vegetable oil worldwide. The U.S. production of
soybean oil was estimated at 8.59 million MT for 2002, of which 7.86 million
MT was consumed domestically. During 2002–2003, Brazil produced 4.90 million
MT and Argentina 4.12 million MT of soybean oil (2). The U.S. price of crude
soybean oil has varied from $0.24/kg to $0.62/kg over the past 5 years with the
lower prices being more recent (1).
Soybeans owe their dominance of the oilseed market to the value of their protein,
which is much greater than that of other oilseeds. Of the oilseed meals produced in
2003, 129.58 million MT out of a total of 185.69 milllion MT was soybean meal
(1). Of the money made on extracting soybeans, the meal accounted for between
51% and 76% of the total in the last 10 years. Soybean oil of typical composition
performs well as a salad oil, but it is usually hydrogenated for use as a margarine
stock or frying oil. Soybean oil’s stability to oxidation also is limited by its content
Bailey’s Industrial Oil and Fat Products, Sixth Edition, Six Volume Set.
Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.
577
578 SOYBEAN OIL
2. COMPOSITION OF SOYBEANS
Table 1 shows the average composition of soybean seed (oil, protein, and some
amino acids) grown in the United States during recent years (3). Aside from varietal
differences, the composition is affected by various geographic/environmental fac-
tors. According to Hurburgh (5), ‘‘oil is much more variable than protein from year-
to-year. States most distant from the center of the Corn Belt (probably those with
the greatest weather extremes) experience the most variability in composition.’’
Table 2 lists some of the environmental and cultivation practices that have an
observable effect on soybean protein and oil percentages. Maestri et al. (6) grew
soybean cultivars in several regions of Argentina and concluded that the protein
and oil contents were positively correlated with altitude. Protein was negatively cor-
related with latitude and precipitation, and oil was negatively correlated with tem-
perature and precipitation. Oil content in soybeans tends to be negatively correlated
with protein, but breeding soybeans for high protein while maintaining oil content
has been a priority of the U.S. soybean producers, and some progress has been
achieved (7, 8). The variety Prolina reportedly produces 22.7% oil and 45.5% pro-
tein on a dry weight basis. There also has been interest in reducing the oligosac-
charides that cause flatulence and reduce the digestibility and nutritive value of
soybeans.
Isoflavones are minor constituents of soybeans whose consumption is believed to
have beneficial effects (9–11). The benefits of isoflavones have encouraged the
direct consumption of soy protein in the United States. The concentration of
isoflavones changes with variety and growing conditions and has been reported
to be 1.2–2.5 mg/g in U.S. beans (9), 0.5–2.3 mg/g in Korean beans (10), and
0.2–3.5 mg/g in Japanese beans (11).
Table 3 shows the typical composition of the lipid phase of soybeans. Triacyl-
glycerols are the primary component. The 3.7% phospholipids content in the soy
beans is higher than that usually found in hexane-extracted oil, which is typically
TABLE 4. The Averages and Standard Deviations of Methyl Esters from Typical Soybean
Oils and the Range Reported for each Methyl Ester.
percentages tend to have reduced oil contents (33, 40, 41). Lines with high stearate
percentages suffer from low yields and sporadically from poor germination. Wang
et al. (42) tested lines with elevated palmitate or stearate in a number of tests of
germination and seedling vigor at three temperatures and found that, although
the high-saturate seed did well in these tests, vigor was negatively correlated
with saturate percentage. Most of the changes reported in Table 4 were attained
by traditional plant breeding or use of mutagenic agents. The high-oleic mutant
is an exception and was attained by direct genetic manipulation (37). High-oleate
lines developed by traditional plant breeding have been reported, but their oleate
percentage varies widely with growth environment, which limits their commercial
value (38).
The fatty acid composition of soybean oil changes considerably with maturity
and with seed oil deposition (15, 35, 43, 44). In typical soybean triacylglycerols,
the palmitate and linolenate tend to decrease with maturity, whereas linoleate
increases. Oleate tends to increase to a maximum and then decline slightly. Soy-
beans selected for atypical fatty acid compositions show quite different patterns
of change with maturity from typical soybeans.
Seitz (31) and Wesolowski (32) measured the saponification and iodine values of
a number of samples from various geographic locations, and their ranges and typi-
cal values are shown in Table 4.
Harp and Hammond (45) explored the stereospecific distribution of acyl groups
on the three positions of the glycerol molecule for soybean triacylglycerols with a
wide range in fatty acid composition. They found that the amount of an acyl group
582 SOYBEAN OIL
on a particular position was linearly related to the amount of that acyl group in the
whole triacylglycerol. At low concentrations of palmitate, stearate, oleate, and
linoleate in the total triacylglycerols, the amounts on the sn-1 > sn-3, but the
reverse was true at higher total concentrations. Palmitate and stearate were confined
to the sn-1 and sn-3 positions, whereas the oleate concentration was similar on all
three positions. Linoleate concentrations at the sn-2 position were generally greater
than those at the sn-1 and sn-3 positions, but the amount of linoleate on the sn-2
position seemed to be strongly and negatively correlated with the amounts of satu-
rates on the sn-1 and sn-3 positions. Plots of linolenate concentrations at particular
positions versus the concentrations in the whole triacylglycerol showed consider-
ably more scatter than plots for the other acyl groups, but they generally showed
the amount of linolenate on sn-2 > sn-1 > sn-3. The saturate percentages also
seemed to influence the amounts of linolenate on the sn-2 position positively and
on the sn-3 position negatively. Table 5 shows the stereospecific distribution of typi-
cal soybean triacylglycerols.
Theoretically, stereospecific data can be used to predict the acylglycerol struc-
ture using the 1-random-2-random-3-random distribution theory (47), if one
assumes the fatty acid composition of the three glycerol positions are individually
controlled but that the combinations of the three positions are random. However,
the change in fatty acid composition with maturity, described in the previous
paragraph, shows that the triacylglycerol composition is unlikely to be truly random
in the combination of the three glycerol positions. In addition, soybeans from the
same plant or pod can have slightly different acyl group compositions, so pooled oil
from many seeds and plants is unlikely to be exactly random in its glycerol position
combinations. Thus, such a calculation can lead only to approximate compositions.
Neff et al. (48, 49) partially separated the triacylglycerols of soybean oils
with a wide range of fatty acid compositions using high-performance liquid
chromatography, and their results are shown in Table 6. These data show how the
amounts of the triacylglycerol species change with fatty acid composition.
The primary phosphatides of soybean oil are phosphatidylcholine, phosphatidyl-
ethanolamine, and phosphotidylinositol, which generally make up 55.3%, 26.3%,
and 18.4% of the total phosphatides, respectively (50). The stereospecific distribu-
tion of the acyl groups in these phospholipids for a typical soybean lipid is shown in
Table 5. In all the phospholipids, the saturated acyl groups are concentrated in the
TABLE 6. Acyl and Triacylglycerol Composition in mol% of Soybean Oils Having a Wide
Range of Fatty Acyl Compositions (48, 49).
Sample Number
——————————————————————————————
Acyl group 1 2 3 4 5
sn-1 position and the unsaturated acyl groups, especially linoleate, on the sn-2 posi-
tion. Phosphatidylinositol tends to be richest in palmitate and stearate, whereas
phosphatidylcholine has the least palmitate. Wang et al. (51) reported the stereospe-
cific distribution of the acyl groups in the various phospholipids types and the
amounts of particular acyl combinations for soybean lipids with a wide variety
of fatty acid compositions. Some phosphatidic acid and lysophospholipids also
may be present as a result of hydrolysis of the phospholipids (52). The amounts
of the hydrolytic products usually increase with age and damage to the beans (53).
Soybeans also contain 170 ! 47 ppm of cerebrosides in which the sugar is glu-
cose and the chief fatty acid is 2-hydroxy palmitic acid (54). Traces of ceramides
also are present. These are believed to play a role in cell signaling in the soybean
plant.
Crude soybean oil contains about 1.9 ppm of Vitamin K1 or phylloquinone (55).
This vitamin plays a role in blood coagulation and bone metabolism. During refin-
ing, some Vitamin K1 may be lost (56, 57), especially during deodorization. Hydro-
genation of the fat converts some of the Vitamin K1 to 20 ,30 -dihydrovitamin K1 (58).
Wilson et al. (7, 8, 39, 59) have reviewed the genetic control of fatty acid bio-
synthesis in soybeans and discussed the advantages of soybean oil with special
compositions. Oil with reduced palmitate is available presently in a limited market.
The commercial introduction of low-linolenate soybeans has been inhibited by the
availability of corn oil, which has a composition like very low-linolenate soybean
oil. The price differential between these oils often is smaller than the costs of con-
tract growing, segregating, and processing low-linolenate soybeans. High-oleate
soybean oil is stable under frying conditions, but this trait alters the flavor of the
fried products (60). The acceptance of high-oleate soybean oil also suffers from
public concern about the growth and consumption of plants produced by direct
genetic modification.
There are small amounts of two acyl groups containing furan rings in soybeans
(30). These oils are reported to be the sources of the odorous compound 3-methyl-
2,4-dione by photo-oxidation (61), but Kao et al. (62) were not able to find differ-
ences in flavor of photo-oxidized varieties with high and low content of these acyl
groups.
The physical properties of fatty acids vary with their chain length, unsaturation, and
other substituents and change with temperature. Numerous attempts have been
made to develop equations that will predict these properties. Soybean oil’s proper-
ties should reflect its constituents and, especially, its fatty acid composition, and
physical properties have frequently been measured for typical soybean oils, but
there have been fewer measurements of soybean oils with modified fatty acid com-
positions.
Table 7 shows the values of physical properties of soybean oil of typical com-
position. Seitz (31) examined 77 samples of soybean oil from various parts of the
PHYSICAL PROPERTIES OF SOYBEAN OIL 585
world over a seven-year period and reported densities at 20% C ranging from
0.9165 g/mL to 0.9210 g/mL. Wesolowski (32) examined the density of 53
Polish soybean oils at 19.9% C and reported values ranging from 0.9202 g/mL to
0.9165 g/mL. The following correlations of density and other variables were found:
with refractive index 0.62, with iodine value $0.64, with saponification value 0.34,
and with acid value 0.59. Yokota and Tachimori (77, 78) also reported a close
relation between density and iodine value. Halvorsen et al. (79) and Rodenbush
et al. (80) developed equations to predict the density of vegetable oils that took their
fatty acid compositions into account and predicted densities of soybean oils with
<0.1% error. The density of vegetable oils changes approximately linearly with
temperature, and Kravchenko et al. (65, 66) found the density decreased
0.000668 g/mL% C between 0% C and 100% C, whereas Alvarado (63, 64) found a
value 0.000643 between 20% C and 70% C, and Noureddini et al. (67) found
0.0006674 between 23.9% C and 110% C.
The densities of soybean oil-solvent mixtures at various temperatures are impor-
tant for engineering calculations and have been reported for hexane, ethylene
dichloride, and tricholoroethylene at 25% C, 37.8% C, and 50% C (81); Skellysolve B
at $20% C, $10% C, 0% C, 10% C, 25% C, and 40% C (82); dichloromethane at 25% C (83);
and hexane at 25% C (84).
The specific heat capacity of soybean oil was measured by Clark et al. (85)
and varied from 0.448 cal/g% C to 0.666 cal/g% C between 1% C and 271% C. Specific
heat increased linearly with temperature at 0.00070 cal/g% C. Tochitani and Fujimo-
to (68) measured the specific heat capacity of soybean oil from about the
586 SOYBEAN OIL
approximate melting point to 150% C and found a linear increase that fit the follow-
ing equation:
where T is the temperature in % C. Their data agreed closely with those of Clark et al.
(85) but were slightly higher than those reported by Kasprzycka-Guttman et al.
(86), who made measurements between 70% C and 140% C. Wang and Briggs (87)
estimated the heat capacities of soybean oils of various compositions based on
an equation by Morad et al. (88). They calculated that high-oleate oils should have
a slightly higher heat capacity and low-saturate oils a slightly lower heat capacity
than typical soybean oil, and the change with temperature should be 0.00057 cal/
g% C. Their equation agreed with their experimental values within !5%.
Miller et al. (73) determined the heat-transfer coefficient for soybean oil at fry-
ing temperatures and found that they varied from 261.3 watts/% KM2 to 276.2 watts/
%
KM2 between 170% C and 190% C, where M2 is square meters of surface.
The melting of natural fats and oils usually occurs over a considerable tempera-
ture range, and soybean oil’s typical melting range is below 0% C. The availability of
differential scanning calorimetry (DSC) at low temperatures has made information
on melting of soybean oil available, and interest in using vegetable oils as fuels has
also sparked measurements of their cloud and pour points. Table 8 (41) gives the
temperatures of onset, maximum, and end of melting for various types of soybean
oil. Table 7 gives the cloud and pour points of typical soybean oil. Wang and Briggs
(87) also gave DSC curves for the melting of high-oleate, low-saturate, and low-
linolenate soybean oil. Hagura and Suzuki (89, 90) used the change in electrical
capacitance of oil samples to obtain the melting range of soybean oil and found
the results agreed with those obtained by DSC.
Seitz (31) measured the viscosity at 20% C of 77 soybean oils from four
geographic locations, and the range of variation was 58.1cP to 62.2cP (Table 7).
Viscosity decreases with temperature, and the relation is not linear. Kinematic
values (viscosity/density) have been reported at 20% C and 80% C by Chioffi (91)
and by Miller et al. (73) at frying temperatures (170–190% C); dynamic viscosities
have been reported between 0% C and 100% C by Kravchenko et al. (65, 66), between
23.9% C and 110% C by Nourreddini et al. (67), between 20% C and 70% C by Alvarado
(63, 64), and between 1% C and 60% C by Arissen (92). Dahlberg et al. (93) were able
to predict the viscosity of soybean and other oils from the Fourier transform infra-
red spectra. Rodenbush et al. (80) calculated the viscosity of oils by relating visc-
osity to a function they termed the reduced density, which they could calculate from
the fatty acid composition.
Several authors have fit their viscosity-temperature data to equations (63–67, 87,
94). Some of these come with a claim of theoretical significance, but all have
enough variables to fit the data well. One of Alavarado’s equations (63, 64) is
ln m ¼ ln m0 þ E=RT; ð2Þ
where E/R was 3262 and ln m0 was $6.997 for soybean oil. Wang and Briggs (87)
reported graphically the change of viscosity with temperature from 10% C to 90% C
for soybeans with altered fatty acid compositions. They found the viscosity of high-
oleic soybean oil higher and low-saturated soybean oil lower than that of typical
soybean oil.
Miller et al. (73) determined the kinematic viscosity of soybean oil at temp-
eratures of 170% C, 180% C, and 190% C, and obtained values of 3.151 cm2/sec,
2.880 cm2/sec, and 2.614 cm2/sec, respectively. The viscosities of soybean oil-hex-
ane (Skellysolve B) mixtures at temperatures between $20% C and 40% C were inves-
tigated by Magne et al. (84). Ibemesi and Igwe (95) examined the reduced viscosity
(viscosity/concentration) of solutions of soybean oil in toluene, xylene, cyclohex-
ane, and tetrahydrofuran. They found an anomalous reduced viscosity increase at
concentrations below about 0.12 g/mL that they attributed to clustering of the fat
molecules in the solvent. Erhan et al. (96) determined the kinematic viscosity of
blends of typical soybean oil with polyalphaolefins and isobutyrl oleate and
high-oleic soybean oil with isotrideceyl adipate and mineral oil to achieve viscos-
ities suitable for lubricants.
The surface tension of soybean oil at 20 –70% C was reported by Alvarado (63, 64)
and is given in Table 7. The surface tension decreased linearly with temperature at
0.077 dyne/cm% C.
Wesolowski (32) examined the refractive index of 53 samples of soybean oil
from Poland, and the range is given in Table 7. Sietz (31) reported average values
for samples from several geographic locations, and these values (1.4747–1.4752)
fall near the mean of Weslowski’s samples. Refractive index depends on chain
length and unsaturation (97) and often has been used to follow hydrogenation
(98–102). Refractive index also has been used to follow autoxidation (103). A clo-
sely related quantity, the dielectric capacitance also has been used to assess the
quality of frying oil (104). Perry et al. (74) measured the vapor pressure of soybean
oil at various temperatures and found that the data fit the equation:
where P is the pressure in microns and T is in K. The also estimated the heat of
vaporization (Table 7).
588 SOYBEAN OIL
Tomoto and Kusano (105, 106) measured the solubility of carbon dioxide,
nitrogen, hydrogen, and oxygen in soybean oil between 0.2 atm and 1 atm and
between 30% C and 70% C. The Bunsen coefficient (volume of gas at standard condi-
tions / volume of soybean oil at 760 mm) at 30% C was 1.018 for carbon dioxide,
0.086 for nitrogen, and 0.048 for hydrogen. The Bunsen coefficient of oxygen at
30% C was 0.141 but increased with temperature, probably because of oxidation
during the measurement. The Bunsen coefficient decreases linearly to zero at
zero gas pressure. The natural logarithm of the Bunsen coefficient versus 1/T in
K is linear, and the constant is the heat of solution of the gases divided by the
gas constant. These heats of solution are $2.42 kcal/mol for carbon dioxide,
$2.58 kcal/mol for nitrogen, and $3.86 kcal/mol for hydrogen. From this relation,
one can calculate the solubility at any temperature and pressure in the range of the
study. Comparison of the values for soybean oil with olive and linseed oil suggested
that the Bunsen coefficients are influenced by the degree of unsaturation of the oil.
The viscosity of soybean oil decreased with the amount of carbon dioxide
dissolved, but dissolved nitrogen slightly increased the viscosity.
Loncin (107) reviewed the data on the solubility of water in fats and oils. For
typical soybean oil, the solubility of water was 0.11% by weight at 22% C and
rose to 0.19% at 60% C. The solubility of water decreases with fatty acid chain
length and increases with the percentage of free fatty acids.
The vapor pressures of soybean oil-hexane mixtures between 75% C and 120% C
were reported (108, 109), and similar data for soybean oil with commercial hexanes
was reported by Smith (110). Arnold and Breuklander (83) measured the boiling
point of dichloroethylene-soybean oil mixtures and found the log (V.P.) was a linear
relation of the mole fraction of oil. Kusano (111, 112) measured the vapor pressure
(P) of soybean oil-solvent mixtures that included hexane, benzene, and carbon tet-
rachloride between 20% C and 50% C and found linear relations between log P and 1/
T. Anikin et al. (113, 114) measured the vapor pressure of mixtures of soybean oil
with the khladon 113 (trichlorotrifluoroethane) between 30% C and 100% C. Aeber-
hard and Spekuljak (115, 116) measured the vapor pressure of hexane in hexane-
soybean oil mixtures and found the vapor pressure at 25% C could be predicted by
the equation
where P is the vapor pressure in Torr and x is the weight percentage of solvent in the
mixture.
Tekin and Hammond (75) measured the resistivity of soybean oil and found it
decreased logarithmically with temperature from about 100 Tohm &cm at $5% C to
0.251 Tohm &cm at 100% C. The resistivity was decreased by saturating the oil with
water and the addition of oleic acid, a-tocopherols, b-carotene, phospholipids, and
monoacylglycerol.
The smoke, flash, and fire points of soybean oil have been determined by the
Cleveland Cup method and show considerable variation. Dickhart (117) reported
a smoke point of 138% C while Detwiler and Markley (76) reported 241–250% C.
GRADING 589
Detwiler and Markley (76) found that the smoke point varied considerably with the
degree of refining, especially the removal of free fatty acids, and also with the mode
of oil extraction. Yen et al. (118) found a smoke point of 191% C, which was raised
several degrees by the addition of phenolic antioxidants. The flash point of soybean
oil, the temperature at which vapors coming from the oil will catch fire from an
ignition source, were reported as 304% C (117), 326–331% C (76), 174% C (69),
318% C (70), and 320% C (119). The low value reported by Ali et al. (69) was
obtained by using a Pensky-Martens closed tester and ASTM method 093-90.
The flash points of hexane-soybean oil mixtures were determined and correlated
with headspace gas chromatography data (120).
Fire points or self-ignition temperatures (SITs) for soybean oil by using the
Cleveland Cup method, which uses a brass cup, were reported to be 356–363% C
(76) and 400% C using a stainless-steel cup apparatus (71). The burning rate of soy-
bean oil was 4.3 g/m2sec, flame height 129 mm, and irradiance 0.153 kW/m2 (71).
Kowalski (119) studied the self-ignition temperature in a differential scanning
calorimeter heated at rates of 40–90% C/min and under 800–2800 kPa of oxygen
pressure and found values of 260–290% C for soybean oil. He found the addition
of copper wire to the sample decreased the self-ignition temperature by 5–15% C.
The self-ignition temperature was inversely related to oxygen pressure. Wakakura
(121, 122) used a scanning calorimeter at an oxygen pressure of 980 kPa with
soybean oil spread on glass wool and in bulk and found self-ignition temperatures
of 147% C and 376% C, respectively.
4. GRADING
To facilitate soybean marketing, the U.S. Federal Grain Inspection Service (FGIS)
established grading standards for soybeans (Table 9) (123), and the FGIS website
(124) provides much more detailed information than can be provided here (124).
TABLE 9. Official Grades and Grade Requirements of the Federal Grain Inspection
Service, United States Department of Agriculture.
Maximum Limits
—————————————————————————
Minimum
Damaged Kernels
Test —————————— Soybeans
Weight Heat Foreign of Other
per Bushel Damaged Total Material Splits Colors
Grade (lbs) (%) (%) (%) (%) (%)
Soybeans are classified into two classes based on color, Yellow Soybeans and
Mixed Soybeans. There are four numerical grades (U.S. No. 1, 2, 3, and 4) and a
U.S. Sample Grade for each class. Sample Grade designates those soybeans that do
not meet the requirements of any of the numerical grades. Six factors are consid-
ered in assigning a grade designation: test weight, amounts of beans that are
damaged or heat damaged, and amounts of foreign material, splits, and soybeans
of other colors. Although important to processors because they affect yields and
qualities of finished products, the FGIS official grades do not consider moisture,
protein, and oil contents, but these factors may be specified on contracts in some
markets. Near infrared transmission (NIT) spectroscopy is widely used to rapidly
estimate (within less than 2 min after sampling and without any sample preparation
required) moisture, protein, and oil contents. Brumm and Hurburgh (125) devel-
oped a computer program to estimate the process value of soybeans based on their
composition and selling prices of oil and meal. In some cases, price premiums are
offered for soybeans high in oil content or high in both oil and protein contents, and
details of the program are available on the Internet (126).
Beans low in test weight may contain less oil. Test weight is the weight in
pounds of grain per Winchester bushel (35.2 L) and is determined by using an Offi-
cial Test Weight Apparatus and a 11/4-quart (1.18 L) sample before removing for-
eign material. All other grading factors are measured as percentages of total sample
weight. Foreign material, which is other grains, weed seeds, pods, leaves, stems,
etc., reduces oil and protein contents and storage life. Foreign material is deter-
mined by sieving a sample. All materials, including soybeans and soybean pieces
that readily pass through an 8/64-inch (3.2-mm) round-hole sieve and all material
other than soybeans remaining on the sieve after sieving are considered to be for-
eign matter. Split soybeans, which result from mechanical damage during handling
and over drying, reduce storage life and oil yield, and increase losses during oil
refining. Splits (typically the cotyledon splits into two halves) and broken beans
(more than two pieces) increase free fatty acid (FFA), phosphatides, iron, and per-
oxide contents of the crude oil. Heat-damaged beans have high-FFA content and
darken the oil color, both changes in oil quality increase refining loss (127). Splits
are defined as beans with more than one-fourth of the bean removed and are not
damaged. Splits are determined by sieving a portion of the grain after removing
the foreign material. Damaged beans reduce the storage life of the beans and oil
yield in processing, cause the oil to be dark-colored and poor in flavor, and increase
losses during oil refining (128). Soybeans and soybean pieces that are badly
damaged by the ground, weather, frost, heat, insects (stinkbug-stung kernels are
considered at one-fourth the actual percentage), mould, or sprouting are considered
to be damaged. Damaged beams are determined by hand picking after removing
foreign material. Soybeans of other colors may affect oil color by contributing
undesirable pigments and are those beans that are green, black, brown, or have mul-
tiple colors.
Almost 27 million MT of soybeans were exported from the United States during
the 2002 crop year, of which 4.8% was U.S. No. 1, 94.6% was U.S. No. 2, 0.4% was
U.S. No. 3, and 0.1% was U.S. No. 4. By comparison, Brazilian soybeans are
RECOVERY OF OIL FROM SOYBEANS 591
typically slightly higher in oil content (6-yr average of 1.2% higher oil content),
foreign matter, damage, free fatty acid, and moisture contents and lower in test
weight (129).
Soybeans are economically important because of their high qualities and quantities
of oil and protein. From one bushel of soybeans (60 lb, 27.2 kg), crushers typically
recover 11.1 lb (5.0 kg) of crude oil, 44.3 lb (20.1 kg) of meal (48% protein), and
3.3 lb (1.5 kg) of hulls with the remainder being shrinkage. According to the U.S.
Department of Agriculture statistics, the oil accounts for about one-third of the
returns in processing soybeans with the protein in the form of meal accounting
for the remainder (130). Over the past five years, the meal (48% protein) has ranged
in yearly average prices of $153–289/MT (6.9–13.1 cents/lb), whereas the oil has
ranged $311–569/MT (14.1–25.8 cents/lb). Hulls have limited outlets, mostly in
cattle feeds, and sell for about $66/MT (3 cents/lb) and return $4.04/MT of
soybeans ($0.11/bu). During the same period, the average price of soybeans in
the United States ranged from $167–270/MT ($4.54–7.35/bu) and crushing
margins, the difference in soybean price and crusher returns, averaged $23.1–
56.2/MT ($0.63–1.53/bu).
Farmers often store their soybeans in metal bins on the farm or in concrete silos
at local elevators for a fee. This allows farmers to sell their crop later in the year
when prices usually increase. Soybeans should be stored at less than 13% moisture
to assure safe storage and preservation of the quality. This moisture content is
usually achieved by drying in the field before harvesting. Lower moisture contents
increase the tendency of soybeans to split during handling to form two half pieces
of cotyledon. Higher moisture content during storage can lead to mold damage or
heating damage due to seed respiration (131). These forms of damage can affect
soybean grade and oil quantity and quality when processed.
The processing of soybeans has been described in more detail elsewhere than
can be done here (132–134). Oil is recovered today by either mechanical means
or through the use of organic solvents. In the preindustrial revolution period, soy-
beans were merely pressed with lever or animal-driven screw-operated batch
presses. Around the turn of the Twentieth Century, when soybeans became a viable
commercial crop in the United States, steam-powered hydraulic batch presses were
used. Today, electric-powered continuous screw-presses, often referred to as
expellers (but this is a trademarked name for screw presses manufactured by one
supplier), or continuous countercurrent solvent extractors are used.
In either case, soybeans are pretreated prior to oil recovery to either make oil
recovery easier or more complete, or to increase the value of the defatted solids
known as meal. Usually, soybeans arriving from the farm or elevator are cleaned
to remove stems, leaves, pods, broken grain, dirt, stones, and extraneous seeds
using shaker screens and aspirators. It is usually advantageous to remove the major
portion of the hulls because they are low in oil (<1%) and protein. The hulls of
592 SOYBEAN OIL
soybeans account for 7–8% of the weight. Dehulling reduces the material going
downstream into costly operations and increases the protein content of the meal.
Dehulling raises the meal protein content by about four percentage points (i.e.,
from 44% for undehulled solvent-extracted soybean meal to 48–49%) and reduces
fiber content (from 7.0% to <3.3%). The formulated feed market prefers high-pro-
tein and low-fiber meal, especially in manufacturing swine and poultry feeds. The
hulls are relatively easy to remove from soybeans compared with those of other oil-
seeds, simply cracking the bean into 6–8 pieces to free the hull using corrugated
roller mills and aspirating the hulls away from the oil- and protein-rich cotyledon,
known as meat, is effective. Consistent bean size is important to proper cracking
and drought-caused shrinking and wrinkling make dehulling much more difficult
and less efficient (135). Often, the aspirated hulls go to gravity tables to scavange
any small meats aspirated with the hulls. Usually, cleaned soybeans are conditioned
prior to cracking to improve dehulling efficiency by heating and drying the beans to
about 9.5% moisture and allowing the moisture to equilibrate for 1–7 days within
the bean to loosen the hull. Various hot-dehulling schemes have also been devised to
increase dehulling efficiency, and are often used in northern latitudes where the pro-
tein contents of soybeans, and, consequently, meal protein levels, may be lower and
specified protein levels cannot be achieved without more complete hull removal.
In the 1930s, soybeans were widely processed by screw pressing after cooking
the seed. A typical process diagram for screw pressing soybeans is shown in
Figure 1 and a plant photo is shown in Figure 2. The beans are heated and the
oil is squeezed out. The pressed oil usually goes to settling basins to reduce fine
Soybeans
Crude Oil
Figure 1. Process flow diagram for screw pressing soybeans.
RECOVERY OF OIL FROM SOYBEANS 593
Figure 2. Photograph inside a modern soybean screw-press plant (courtesy of West Central
Cooperative, Ralston, IA). (This figure is available in full color at http://www.mrw.interscience.
wiley.com/biofp.)
solids content, with the fines being recycled to the screw press. The oil then goes to
polish filters before being placed into storage for shipment to a refinery. Today, in
the United States, there are less than a half-dozen traditional screw press plants
(excluding extrusion-expelling, which will be discussed later). Only one screw-
press plant crushing more than 800 MT/day exists, and it is located in Ralston,
IA. Under optimum processing, the meal can contain as low as 4–6% residual
oil, which contributes metabolizable energy to livestock consuming screw-pressed
meal. As a result of the heat treatment during cooking and screw pressing,
increased rumen-bypass characteristics improves feed efficiency in high producing
dairy cattle. Thereby, the meal may sell for premium prices over solvent-extracted
meal when adequate numbers of dairy animals are located nearby. As this meal is
used to feed ruminants, the beans are not usually dehulled.
Direct solvent extraction is the most widely used oil-recovery method for
soybeans, but it also requires considerable capital and large scale to compete. In
actual practice, solvent extraction is used to crush over 98% of the soybean pro-
cessed in the United States. Process flow diagrams are shown in Figures 3 and 4.
Most soybean solvent-extraction plants process more than 2,500 MT/day (Figure 5),
and some are capable of processing as much as 5,000 MT/day (especially newly
constructed plants in Brazil). Direct-solvent-extraction plants smaller than 1,000
MT/day have difficulty competing in the United States. At various times, soybeans
have been extracted commercially with petroleum distillate fractions that resemble
gasoline, acetone, carbon disulfide, ethanol, trichloroethylene, and even water,
594 SOYBEAN OIL
Soybeans
CRACKING
ASPIRATING GRAVITY Hulls
TABLING
( optional)
Meats
Cracked Meats
CONDITIONING
FLAKING
Flakes
EVAPORATING EXPANDING
( optional)
Solvent
Miscella Collets
(oil and solvent)
SOLVENT
STRIPPING
EXTRACTING
GRINDING
MEAL Enzyme-active
DESOLVENTIZING Flour
TOASTING
COOLING
GRINDING
Toasted Meal
Figure 3. Process flow diagram for direct solvent-extracting soybeans.
which is not a true solvent but facilitates oil separation by creaming. A petroleum
distillate containing a mixture of hexane isomers having a typical boiling range of
65% C to 71% C is the only solvent used today. These products typically contain 45%
to 70% n-hexane. n-Hexane is considered a neurotoxin in the United States and has
proven toxicity at high concentrations. The U.S. Occupational and Safety Admin-
istration has set the maximum workplace exposure level at 500 ppm and a time-
weighted average not to exceed 50 ppm (136). In recent years, there has been con-
siderable interest by the soybean industry in alternative solvents to hexanes because
of increasing environmental and safety concerns. Alternative solvent technologies
have been extensively reviewed (137–139).
Figure 4. Depiction of equipment and process flow diagram for direct solvent-extracting soybeans (courtesy of French Oil Mill Machinery Co., Piqua, OH).
595
596 SOYBEAN OIL
Cleaned and dehulled soybeans are conditioned by heating to 74% C to soften the
meat prior to flaking using smooth roller mills. Proper cracking and conditioning
are important to achieve the desired cell distortion or cell rupture that is necessary
for efficient extraction and to prevent production of excessive amounts of fine meat
particles that impede proper flaking or extraction. Highly distorted cells are desired
(140) so that cell walls and pseudo-membranes around oil bodies are sufficiently
ruptured, and the oil can be easily contacted by the solvent and leached out. Soy-
beans are typically flaked to 0.25 mm (10–12 thousandths of an inch) to achieve the
desired distortion (141). The flakes may be conveyed directly to the extractor or to
an expander. In recent years, expanders have been adopted to achieve increased cell
distortion and to produce an easily extractable porous pellet (collets) that is more
dense than flaked soybeans. Thereby, more mass of material can be placed into the
fixed volume of the extractor, the oil is more quickly extracted reducing extraction
time, and the solvent drains more completely reducing the load on meal desolven-
tizing equipment. All of these factors increase plant throughput capacity (142–144).
Plants vary in the amounts of flakes that are expanded, typically about one-third of
the flake production, but in a few cases, all flakes are expanded. Although there is
not universal agreement, expanding may also improve oil quality by quickly inac-
tivating phospholipases, which cause phospholipids to become nonhydratable. In
the author’s opinion, adoption of expanders is the most significant change in solvent
extraction during the past quarter century.
RECOVERY OF OIL FROM SOYBEANS 597
solvent to less than 0.2% remaining in the oil. The temperature of the oil in the
stripper should not exceed 115% C to prevent scorching the oil and causing dark col-
or. Flash point determination is an easy method to assure that the solvent-evapora-
tion equipment is operating as it should and the flash point should exceed 150% C.
All evaporated solvent is recycled to the extractor. The oil should be sent to a
vacuum dryer to remove any residual stripping steam condensate and the dry oil
immediately cooled prior to placing into storage.
As a result of natural antioxidants (i.e., phoshpahtides, tocopherols), crude soy-
bean oil can be stored for a long time in large tanks provided the oil is first cooled to
ambient temperature and has limited access to air. The crude oil should be low in
moisture to prevent hydrolysis. Gummy deposits of phosphatides may spontaneously
form in the bottoms of storage tanks and tank cars used for shipping crude oil.
There has been much speculation about using supercritical carbon dioxide
because using this technology eliminates safety issues as carbon dioxide is not
flammable and the oil is better quality (139), but no such plants have been con-
structed to process soybeans. This is due to the absence of a commercially feasible
means of continuously feeding soybean flakes into a high-pressure vessel and
removing the spent flakes. Recently, one company has developed a screw press in
which supercritical carbon dioxide is injected into the barrel. This equipment has been
successfully used to produce soybean meal with lower residual oil contents than typi-
cally produced by screw pressing and with little heat denaturation of the protein.
The spent flakes or collets are sent to a meal desolventizer-toaster (DT). Newer
equipment incorporates countercurrent steam usage. The Schumacher-type deso-
lventizer/toaster/dryer/cooler has become widely accepted in the soybean industry,
and, with this equipment, residual levels of hexane should be less that 500 ppm.
Both indirect and direct steam heating are used. Steam vapor and a modest vacuum
carry away the solvent vapors for condensing. Condensed solvent is recycled to the
extractor after separating water from the hexane. A desolventizer-toaster is a series
of trays through which the meal flows. Soybean meal is unique in that it must be
toasted to inactivate protease inhibitors (especially trypsin inhibitor) that would
reduce feed efficiency if not denatured and inactivated. Urease activity is used as
a measure of adequate heating. The toasted meal typically has low-protein solubi-
lity as measured by protein dispersibility index (typically 45 PDI). The meal is then
sent to a dryer-cooler to reduce the meal temperature for safe storage. The moisture
content should be about 12% and the residual fat content less than 1.5%. The free
extractable oil after extraction is less than 1.0%, but heating during desolventizing-
toasting frees some bound fat that previously was not extractable with hexane.
Overtoasting may reduce digestibility and nutritional value of the meal. The meal
is then ground with a hammer mill to produce meal with uniform particle size.
If dehulling is employed, as is typical for plants in the United States, the meal
will contain around 48% protein. Additionally, dehulling reduces the fiber content
of the meal by over 50%. In some plants, a portion of the soybean hulls may be
added back to the meal prior to grinding to adjust and precisely control meal protein
content. Livestock feeders are concerned about having uniform protein and fiber
contents in order to formulate minimum-cost feeds for maximum feed efficiency.
RECOVERY OF OIL FROM SOYBEANS 599
The meal is generally ground so that 95% passes a U.S. 10-mesh screen and a max-
imum of 3% to 6% passes through a U.S. 80-mesh screen.
Some plants divert part of their spent flake production away from a desolventi-
zer-toaster to a flash desolventizer, which is designed to produce white flakes with
high-protein solubility (PDI 70 –90). White flakes are used as the starting material
for producing protein isolates or concentrates, which contain >90% and 65% pro-
tein, respectively, and are used as food ingredients.
Some soybean extraction plants also degum their oil before shipping to centra-
lized refineries. There is not sufficient market to make it profitable to recover all of
the soybean phosphatides and market them as soy lecithin. The gums are added
back to the meal in the toaster to evaporate the water. The gums contribute to
the metabolizable energy content of the meal and the soybean crusher can get
meal prices for crude phosphatides.
Quality standards and trading rules for solvent-extracted soybean meal and oil
are designated by the National Oilseed Processors Association and are available
at a website (145). Soybean products are remarkably uniform in their quality char-
acteristics compared with alternative sources of oil and meal.
Recently, a third process, known as extruding-expelling (or Express Systems as
trademarked by the equipment manufacturer), was developed (Figures 7 and 8)
(146, 147). In this process, a dry extruder, which generates heat solely through fric-
tion of the beans in the extruder, replaces steam generating and steam heating the
beans. The heated beans then go to a screw press and the rest of the process is
the same as in screw pressing. The plants typically process 5–50 MT/day.
Soybeans
EXTRUDING
EXPELLING Cake
Foots (screw pressing) MEAL GRINDING
Crude Oil
Figure 7. Process flow diagram for extruding-expelling soybeans.
600 SOYBEAN OIL
Approximately 70 extruding-expelling plants have been built over the past 10 years
for crushing soybeans. Usually, these plants are farmer-owned and provide meal to
nearby livestock feeders (148). The oil is sold to the large oil refineries, often at a
discount despite the oil being of excellent or superior quality because high costs are
incurred in handling small lots of oil. These plants are ideally suited to identity-
preserved processing. There are niche opportunities for these plants to market
certified organic or nonGMO soybean oil, for which there is a lucrative market
in some countries. Other opportunities reside with genetically enhanced soybean
oils and meals, such as low-linolenate, high- and low-saturates, and high-oleate
oils. This process has even been proposed for producing soybean products during
interplanetary exploration (149). NASA plans to grow soybean in space because
some missions, such as Mars exploration, cannot be supported without growing
food in space.
Wang and Johnson (150) compared the qualities of soybean oils and meals obtained
by the three processing methods. Soybean oil and meal samples were collected
at three times within a one-year period from 13 extruding-expelling plants, eight
QUALITIES OF SOYBEAN OILS AND MEALS EXTRACTED 601
Processing Method
—————————————————————————————
Property Solvent Extraction Screw-Pressing Extruding-Expelling
solvent-extraction plants, and one continuous screw-press plant. Their results are
shown in Tables 10 and 11. Solvent extraction is by far the most efficient method
of recovering oil from soybeans, typically only about 1.2% residual oil is left in the
meal. Screw-pressing is slightly more efficient in recovering oil than is extruding-
expelling, leaving 6.3% oil in screw-pressed meal compared with a mean of 7.2%
for extruded-expelled meals. Most solvent-extraction plants dehull soybeans to pro-
duce soybean meal with 48% or more protein and carefully control the moisture
content at 12%. Solvent-extracted soybean meal is highly uniform, often much
more so than either screw-pressed or extruded-expelled meal. The high-protein
and low-fiber contents of solvent-extracted soybean meal are desired when feeding
poultry and swine, which consume 46% and 25% of the soybean meal produced,
respectively. Most extrusion-expelling and screw-press plants have not invested
in dehulling equipment, as their meal generally goes into feeding ruminant animals.
Protein dispersibility indices, a measure of protein denaturation that is used in
the food industry, are lower for extruded-expelled and screw-pressed meals. Protein
Processing Method
—————————————————————————————
Property Solvent Extraction Screw-Pressing Extruding-Expelling
Defatted soybean meal (white flakes) may be heated to produce a variety of solu-
bility and enzyme-activity characteristics, ground and sized to produce grits or
flour, and used as a food ingredient in bakery products, soymilk, and meat products.
A historical accounting of the development of these products was published by
Johnson et al. (151, 152). Soy flour may be relecithinated or refatted with refined,
bleached, and deodorized oil to achieve desirable functional properties. Soy flour
can also be texturized by using an extruder to produce meat-like products called
TVP (texturized vegetable protein) that are often used to extend ground meat.
Enzyme-active soy flour is used in bread at 0.5% of the wheat flour. Lipoxygenase
in the soy flour bleaches the carotenoids of wheat flour to produce a whiter crumb
and improves dough-mixing properties. White flakes may be processed into soy
protein isolates or concentrates (132, 153). Soy protein is poorly soluble in water
at pH 4.5, the isoelectric point, and highly soluble at pH >8.0. These solubility
characteristics can be used to isolate or concentrate soy protein.
Untoasted and flash-desolventized meal in which the protein is undenatured and
highly soluble (>70 PDI and preferably >90 PDI) is the preferred starting material
in manufacturing soy protein isolates. Under some conditions, extruded-expelled
meal can be used, but the yield of soy isolate is reduced. The meal is ground in
water adjusted to pH 8.0 with sodium hydroxide and centrifuged to remove insolu-
ble fiber. The soluble fraction is acidified to pH 4.5, and the protein precipitates.
The precipitated protein curd is separated from the soluble sugars by centrifuging.
The protein curd may be washed, neutralized, and spray-dried.
High protein solubility is not needed for protein concentrates and heating to
insolubilize the protein and facilitate extracting the solubles (mostly sugars) with
water is one way that has been used to prepare soy protein concentrates. Concen-
trates today, however, are normally made by extracting the sugars with either acid
(pH 4.5) or aqueous ethanol (60–80%). Aqueous ethanol is most frequently used
because it produces the blandest product, but ethanol denatures the protein and
leaves the protein with reduced functional properties unless the product is refunc-
tionalized by jet cooking (154, 155) or by homogenizing under alkaline conditions
(156). Soy protein concentrate must contain >65% protein on a dry basis.
The soybean storage proteins glycinin and b-conglycinin, which often are recog-
nized in the older literature as 11S and 7S proteins, respectively, based on their
sedimentation during ultra centrifuging, comprise 65–80% of the protein. Methods
have even been developed to separate soy protein into fractions rich in individual
proteins (157, 158). Some believe b-conglycinin has greater health benefits than
glycinin.
Soy protein isolates are used in dairy analogs (milk replacers and beverage pow-
ders), meat-pumping solutions, luncheon meats, and infant formulas, whereas soy
protein concentrates are used in dairy analogs (milk replacers, beverage powders,
cheeses, coffee whiteners, frozen desserts, whipped toppings), baked goods, and
meat products (156). These protein products are used for their functional properties
such as solubility, water absorption and binding, viscosity control, gelation,
604 SOYBEAN OIL
As discussed in the previous section on soybean oil composition and Table 11,
crude soybean oil can contain phospholipids, free fatty acids, lipid oxidation
products, and unsaponificable matter, which includes chlorophyll and carotenoid
pigments, tocopherols, sterols, and hydrocarbons. Some of these components nega-
tively affect oil quality, and some may play positive roles in nutrition and function-
ality. The goal of oil refining is to remove the undesirable components so that a
bland, stable, and nutritious product can be obtained. The basic processing opera-
tions in oil refining are (1) degumming, (2) neutralization, (3) bleaching, (4) hydro-
genation, (5) deodorization, and (6) winterization or crystallization. These steps are
outlined in a flow chart as shown in Figure 9.
8.1. Degumming
Crude soybean oil contains a relatively high concentration of phospholipids com-
pared with other vegetable oils. Degumming is a process of removing these com-
ponents from crude soybean oil to improve its physical stability and facilitate
further refining. Phospholipids can lead to dark-colored oils and they can also serve
as precursors of off-flavor (162) compounds. Free fatty acids, pigments, and other
impurities are also partially removed by degumming. Soybean oil can also be neu-
tralized directly without degumming if gum or lecithin recovery is not desired. Con-
ventional belief holds that the loss of neutral oil in refining crude oil by direct
neutralization is less than the combined losses of degumming and caustic refining
of the degummed oil.
The quality of crude soybean oil influences the efficacy of degumming. Phos-
pholipids can exist in a hydratable form, which can be readily removed by addition
BASIC PROCESSING OPERATIONS 605
Water
FILTERING Foots
GUMS HYDRATING CENTRIFUGING
Alkali NEUTRALIZING
Soapstock GUMS DRYING Moisture
CENTRIFUGING (free fatty acids,
phosphatides)
Water WASHING Lecithin
Wash-water
CENTRIFUGING (residual
soapstock)
VACUUM DRYING Moisture
Bleaching BLEACHING
Earth
Spent Bleaching
FILTERING Earth (color, residual
soapstock)
Steam DEODORIZING DISTILLATE CONDENSING
8.2. Neutralization
Neutralization is also referred to as de-acidification and alkali or caustic refining.
Neutralization is achieved by treating the soybean oil with aqueous alkaline solu-
tion (most commonly, sodium hydroxide) to neutralize the free fatty acids in a batch
or continuous system. The soap formed in the reaction also adsorbs natural pig-
ments, the gum and mucilaginous substances not removed by degumming. Natural
settling or centrifugation is used to remove the soap. Crude soybean oil also can be
netralized directly without degumming. When this is practiced, the oil commonly is
pretreated with 300–1000 ppm of 75% phosphoric acid to facilitate removal of
phospholipids. The percentage of excess sodium hydroxide solution required for
crude oil is higher than that for degummed oil (173).
The quality changes, such as lipid oxidation and reduction of tocopherols and
phytosteols during neutralization, are considerable compared with the other proces-
sing steps as shown by Wang and Johnson (174), and also as presented in Table 12.
The further phospholipid removal (below 2 ppm phosphorus) also reduces the oxi-
dative stability of soybean oil (175) due to the antioxidant property of these phos-
pholipids.
One of the new developments in neutralization is the use of silica-based adsor-
bent to remove the residual soap instead of using water washing. Water usage and
BASIC PROCESSING OPERATIONS 607
waste generation is greatly reduced by this practice. Sodium silicate also was used
as a mild neutralizing agent to refine specialty oils (176). Its agglomerating ten-
dency allowed the removal of the soap by filtration, and its low alkalinity mini-
mized saponification of neutral oil and loss of minor nutrients. Other adsorbents,
such as magnesium silicate, also were shown to be effective in reducing free fatty
acids, as well as reducing primary and secondary oxidation products in the treated
oil (175, 177).
Physical refining or steam refining is a process similar to steam deodorization.
Steam distillation is typically used for oil with a high free-fatty acid content to
reduce the refining loss, which would be significant if caustic refining was used.
Acid-aided degumming produces soybean oil with very low phosphorus content
and makes the distillation of free fatty acids possible. Nevertheless, the relatively
difficult task of removing sufficient phospholipids from soybean oil has prevented
extensive use of this technique in the United States. Physical refining, however, has
virtually replaced caustic refining of palm oil in Malaysia.
8.3. Bleaching
Bleaching is a process designed not only to remove the oxidation-inducing pig-
ments such as chlorophylls, but more importantly to decompose the peroxides pro-
duced by oxidation into lower molecular weight carbonyl compounds that can be
removed by subsequent deodorization. Bleaching also removes other impurities
such as soap and metal ions. In soybean oil refining, color reduction occurs at
each step, nevertheless, the most significant reduction of chlorophylls occurs in
the bleaching step. Acid-activated bleaching clay is most effective in adsorbing
chlorophylls and decomposing peroxides, and it is commonly used for soybean
oil. The chlorophyll content in normal crude soybean oil (1–1.5 ppm) can be
reduced by 25% by alkali refining, and bleaching with acid earth further reduced
chlorophylls to 15 ppb (178) The subsequent hydrogenation and deodorization
remove or degrade red and yellow pigments more than chlorophyll, so incomplete
chlorophyll removal by bleaching will cause the refined oil to appear greenish. The
refined and bleached oil is particularly susceptible to oxidation and is less stable
than the crude, degummed, refined, or deodorized oils (178).
608 SOYBEAN OIL
The desired bleaching endpoint is typically zero peroxide, although a color spe-
cification is often used as an important measure. The amount of bleaching earth
should be adjusted based on the quality of oil to be bleached, and it usually ranges
from 0.3% to 0.6% for a typical soybean oil. Low contents of phosphorus (5–10
ppm P) and soap (10–30 ppm) in the neutralized oil are essential to maximize
the bleaching effect. Successful bleaching can be achieved by atmospheric batch
bleaching, vacuum batch bleaching, or continuous vacuum bleaching at tempera-
tures between 100% C and 120% C for 20–30 min. More details of soybean oil bleach-
ing are described by Erickson (179).
Recently, silica-based synthetic materials have been used in bleaching. The nat-
ural bleaching earth, fuller’s earth, a hydrated aluminum silicate, mostly has been
replaced by acid activated clays, which are sulfuric- or hydrochloric-acid-treated
bentonites or montmorillonites. Manufacturers continuously improve the quality
and develop new bleaching earths to meet the market’s needs. Higher activity
and filterability are the main focuses of such development.
8.4. Hydrogenation
The high degree of unsaturation, particularly the relatively high content of linole-
nate, of soybean oil significantly limits its food applications because of low oxida-
tive stability. Hydrogenation is used to improve oxidative stability as well as to
increase the melting temperature of soybean oil. A great proportion of soybean
oil is hydrogenated to produce cooking oil, bakery/confectionery fats, and shorten-
ing.
When oil is treated with hydrogen gas in the presence of a catalyst (typically
nickel) and under appropriate agitation and temperature conditions, it becomes
more saturated and forms a semisolid or plastic fat that is suitable for many food
applications. Selectivity is a term used to describe the relative reaction rate of the
fatty acids from the more unsaturated to the more saturated forms. Perfect selectiv-
ity would provide sequential elimination of linolenate, linoleate, and then oleate. To
completely hydrogenate linolenate while minimizing changes in the other acyl
groups, a high ratio of the reaction rates of linolenate to linoleate compared with
linoleate to oleate is desirable. Generally, selectivity increases with temperature and
catalyst concentration and with decreases in hydrogen pressure and agitation rate
(180). The effect of pressure on hydrogenation selectivity of soybean oil was
reported by List et al. (181), who found that the linoleate-containing triacylglycer-
ols were reduced at a slower rates than the linolenate-containing triacylglycerols
under selective condition. At higher pressures (500 psi), the reaction was truly non-
selective; whereas at 50 psi, the reaction became selective. Impurities in soybean
oil, such as phosphorus, oxidation products, carotene, and metal ions can poison
the catalyst and cause slower hydrogenation (182). A particular limitation with
nickel catalyst is its low selectivity for linolenate over linoleate, and copper-con-
taining catalysts have greater selectivity for linolenate acid than the conventional
nickel catalysts (183). The use of copper catalyst can produce soybean oil that
has a low degree of hydrogenation (iodine value of 110–115) but has less than
BASIC PROCESSING OPERATIONS 609
1% linolenate. However, copper catalysts are not as active as nickel catalysts; they
are also easily poisoned (184). Furthermore, any trace of residual copper in the fully
processed oil will promote lipid oxidation.
The most common tests for degree of hydrogenation are congeal point and the
iodine value as determined by refractive index. Refractive index is a valuable tool
for iodine values above 95, but when the oil is further hydrogenated, refractive
index becomes an inadequate measurement for melting prediction because
increased amount of trans-isomers results in harder oil than the refractive index
would indicate (185). For margarine or shortening, the solid fat index (SFI), as
determined by dilatometry, or solid fat content (SFC), determined by nuclear mag-
netic resonance, is the most appropriate method to measure the consistency of the
hydrogenated oil. These indices predict the workability and creaming ability at a
particular temperature.
Double-bond isomerization or trans-fatty acid formation is the most important
side-reaction that occurs during hydrogenation, and it has a strong impact on the
physical and possibly the nutritional properties of the products. Trans-double bonds
are thermodynamically a more favorable configuration than their cis-counterpart; so
trans-bonds are produced in significant quantities if the hydrogenation does not go
to completion. The trans-fatty acids have a much higher melting point than their
cis-isomers, therefore a fat product with considerable trans-acyl groups will have
an elevated melting point, which is desirable in shortening and margarine applica-
tions. A partially hydrogenated soybean oil can have at least 30 different one-, two-,
and three-double-bond isomers that will result in more than 4000 different triacyl-
glycerol molecules. This complexity allows the production of a great variety of oils,
margarines, and shortenings that have a wide range of physical and functional prop-
erties. However, the established relationship between trans-fat consumption and
health has prompted research to minimize trans-double formation in fats and oils.
Hydrogenation of soybean oil may be carried out in a batch or a continuous sys-
tem. In the United States, batch operations are typical. More comprehensive
reviews on hydrogenation and formulation can be found in Erickson and Erickson
(180), Hastert (186), and Kellens (187).
8.5. Deodorization
Deodorization is usually the last step in conventional oil processing. It is a steam-
stripping process in which good quality steam (1–3% of oil) generated from de-aer-
ated and properly treated feed water is injected into soybean oil under high tem-
perature (252–266 % C) and high vacuum (<6 mm Hg) to decompose peroxides
and vaporize the free fatty acids and odorous compounds. Deodorization relies
on the large differences in volatility between the triacylglycerols and other undesir-
able components under certain conditions. The musty and earthy odor produced
from bleaching and the hydrogenation odor and flavor are effectively removed by
deodorization. The free fatty acids, typically ranging from 0.1% to 0.5% in neutra-
lized oil and 0.5% to 5% in oil to be physically refined, are also reduced to below
0.03%, a value used as an indicator for deodorization efficiency. Zero peroxide
610 SOYBEAN OIL
stability of soybean oil at different stages of refining indicated that crude oil was the
most stable and highly purified oil was the least stable (192). The influence of the
refining steps on the distribution of free and esterified phytosterols in soybean and
other oils was reported by Verleyen et al (193). A significant reduction in free ster-
ols was found after neutralization. Deodorization removed free sterols and also pro-
moted steryl ester formation when the oil was physically refined due to a heat-
promoted esterification reaction between free sterols and free fatty acids.
Alternative techniques are being developed for refining soybean oil produced by
mechanical means. Simple refining methods were explored to process extruded-
expelled (E-E) soybean oils with various fatty acid compositions (174, 177). E-E
oils can be easily water degummed to very low phosphorus levels. Free fatty
acid content was reduced to 0.04% by adsorption treatment with Magnesol1, a
commercial magnesium silicate product from Dallas Group of America (Jefferson-
ville, IN). This material also adsorbed primary and secondary oil oxidation pro-
ducts. A mild steam deodorization as the last processing step produced good-
quality soybean oil. This adsorption refining procedure was much milder than con-
ventional refining, as indicated by little formation of primary and secondary lipid
oxidation products and less loss of tocopherol during refining.
10.1. Lecithin
Soybean lecithin is the predominant source of food and pharmaceutical lecithin
because of its availability and outstanding functionality. The composition of crude
soy lecithin is shown in Table 14. As a result of the presence of a large amount of
neutral oil, crude lecithin is usually de-oiled to improve its functionality. De-oiling
is based on the solubility difference of neutral and polar lipids in acetone, in which
the phospholipids are precipitated and separated. Alcohol fractionation of de-oiled
lecithin can further separate lecithin into an alcohol-soluble fraction that is enriched
with phosphatidylcholine and an alcohol-insoluble fraction enriched with phospha-
TABLE 14. Composition of Commercial Soy Lecithin in Comparison with Egg Lecithin,
wt % (195).
Phosphatidylcholine 29 60 4
Phosphatidylethanolamine 29 30 29
Phosphatidylinositol and glycolipid 32 2 55
Neutral oil 3 4 4
Others 7 4 8
Emulsion type favored w/o or o/w o/w w/o
Soybean tocopherols are the major source of natural fat-soluble antioxidants and
Vitamin E. The Vitamin E activity of natural d-a-tocopherol is much greater that
that of synthetic Vitamin E, which is a mixture of eight stereoisomers (203). Phy-
tosterols are used as raw materials for over 75% of the world’s steroid production.
The more recent application of phytosterol, phytostanol, and their fatty acid esters
in margarine and table spreads is based on the blood cholesterol-lowering effect of
these compounds (204, 205). The recent development of functional foods containing phy-
tosterols has been reviewed by Hollingsworth (206) and Hicks and Moreau (207).
The preparation of high-purity tocopherols and phytosterols involves steps such
as molecular distillation, adduct formation, liquid-liquid extraction, supercritical
fluid extraction, saponification, and chromatography (175). The extraction of toco-
pherols from soybean oil deodorizer distillate by urea inclusion and saponification
of free fatty acids resulted in good recovery of tocopherols (208). To improve the
separation of sterols and tocopherols, Shimada et al. (209) used a lipase to esterify
sterols with free fatty acids. Then the steryl esters and tocopherols were separated
better by molecular distillation. Chang et al. (210) used supercritical fluid CO2
extraction to recover tocopherols and sterols from soybean oil deodorizer distillate.
A patent by Sumner et al. (211) advocated treatment of the distillate with methanol
to converted free fatty acids and other fatty acid esters to methyl esters that can then
be removed by a stripping operation. Then separation of sterols and tocopherols
could be carried out by molecular distillation.
10.3. Soapstock
Soap is recovered from alkaline neutralization of the crude or degummed soybean
oil. Soap consists of water, free fatty acids, neutral oil, phospholipids, unsaponifi-
able matter, proteins, and mucilaginous substances. Its composition depends on
seed quality and oil extraction and refining conditions. Soapstock is the least valu-
able byproduct from oil processing, and it is generated at a rate of about 6% of the
volume of crude soybean oil refined (212), amounting to as much as 0.8 million MT
in the United States annually. The majority of the soap or acidulated soap is used as
a feed ingredient contributing metabolizable energy. Soybean oil can be refined
using potassium hydroxide and acidulated with sulfuric acid, followed by neutrali-
zation with ammonia rather than sodium hydroxide to produce a fertilizer (213).
Soybean oil methyl esters can also be produced from soapstock (214–218) for bio-
diesel applications.
uses, about 48% (3.89 million MT, 8,570 million pounds) was for shortening, 43%
(3.58 million MT, 7,897 million pounds) for cooking and salad oils, 7% (0.56 mil-
lion MT, 1,237 million pounds) for margarine, and 1% (0.06 million MT, 125 mil-
lion pounds) for other food uses. Soybean oil is used to produce about 95% of the
total margarine and 83% of the total shortening consumed in the United States.
Among the 0.24 million MT (519 million pounds) used in nonfood products,
about 16% (0.04 million MT, 85 million pounds) was for resins and plastics,
12% (0.03 million MT, 60 million pounds) for paint and varnish, 13% (0.03 million
MT, 68 million pounds) for fatty acids, and 59% (0.14 million MT, 306 million
pounds) for a myriad of other inedible uses. The use of soybean oil in lubricants
(220), oleochemicals (221), and bioplastics (222), and the production of methyl
soyate for environmentally friendly solvents (223, 224) and for blending with diesel
fuel to produce biodiesel (20% methyl soyate/80% diesel fuel) (225) are significant
parts of the soy oil used in nonfood applications (226). Usage of soybean oil to
make biodiesel is likely to increase in future years because several new plants
are planned for construction as a result of the recent Farm Bill of 2002 providing
financial incentives for producing biobiesel. Some states, notably Minnesota, have
enacted legislation that provides biodiesel tax incentives. Biodiesel interests have
become organized as the National Biodiesel Board (Jefferson City, MO) and the
Renewable Fuels Association (Washington, DC), and exercise considerable politi-
cal influence. During 2002, 57 million liters (15 million gal) of biodiesel were pro-
duced in the United States (227), almost three times that which was produced in
2001.
The usage of soybean oil in food products is similar to other oils, and these uses
and products are discussed in more detail for all oils in other chapters of this edi-
tion. This chapter will focus on specifics of soybean oil in those uses. The major
products in which soybean oil is consumed are cooking and salad oils, frying oils
and fats, baking shortenings, and margarine. Only minor amounts of soybean oil are
used in vegetable dairy products and confectionery products.
TABLE 16. Trading Specifications for Crude Degummed, Once-Refined and Fully Refined
Soybean Oils (228).
Methods of
Factor Crude Degummed Once-Refineda Fully Refineda Analysisb
Moisture and volatile 0.3 max.c 0.10 max. 0.10 max.d Ca 2d-25
matter and
insoluble impurities (%) (up to 0.15 with (up to 0.15 with Ca 3a-46
discount) discount)
Flash point (% C) 121 min. 121 min. Cc 9c-95
Free fatty acids 0.75 max. 0.10 max. 0.05 max. Ca 5a-40
(% as oleic)
(up to 1.25 with (up to 0.15 with
discount) discount)
Unsaponifiable 1.5 max. 1.5 max. 1.5 max. Ca 6a-40
matter (%)
Presence of fish and Neg. 28.121
marine animal oils
Phosphorus (%) 0.02 max. Ca 12-55
(up to 0.025 with
discount)
Refined bleached color 3.5 Red max. 20 Yellow, 2.0 Cc 8e-63
(Lovibond) Red, max. Cc 13b-45
Green color None
Flavor Bland
Cold test (hr) 5.5 min. Cc 11-53
Peroxide value 2.0 max. Cd 8-53
(meg/kg)
AOM Stability 8 min. Cd 12-57
(hr to 35 PV)
a
The oil shall be clear and brilliant in appearance at 21–29% C (70–85% F) and free from settlings in this
temperature range.
b
Analyses in accordance with the Official and Tentative Methods of the American Oil Chemist’s Society except
for presence of fish and marine animal oils in accordance with Association of Official Analytical Chemists
methods.
c
Includes insoluble impurities as determined by AOCS Method Ca 3-46.
d
Oil shall be free of settlings or foreign matter of any kind.
oils, however, reflect their differences in oxidative and thermal stabilities. Cooking
and frying oils need to be more stable to oxidation than salad oil because of the
higher temperatures to which cooking oils are exposed. Temperature stability is
especially required in fats and oils used in deep-fat frying. Salad oils must be phy-
sically stable so that they do not crystalize at refrigerated temperatures.
As soybean oil contains relatively great amounts of the polyunsaturates, notably
unstable linoleate (61%) and linolenate (7.8%), partial hydrogenation is customary
to make cooking or salad oils more stable to oxidation. Typical specifications for
different cooking and salad oils are shown in Table 17.
Synthetic antioxidants, such as butylated hydroxyanisole (BHA), butylated
hydroxytoluene (BHT), propyl gallate (PG), ascorbyl palmitate, and tertiary-butyl-
hydroquinone (TBHQ), are used in soybean cooking oils and frying fats (230).
These antioxidants are typically added at 0.01% for one antioxidant and 0.02% total
for two or more. Natural antioxidants, derived from sage, rosemary, and green tea,
are increasingly popular because of consumer preferences for natural food ingredi-
ents (231).
Salad oils differ from cooking oils in their tolerance to cold temperatures with-
out crystallizing. Salad oils must not crystallize, cloud, or leave deposits of any kind
when stored at refrigerator temperatures (4.4% C) and are defined as such. Soybean
oil used as a salad oil should not cloud or produce any visible crystals and remain
brilliant and clear for a minimum of 5.5 hr at 0% C. Fully refined soybean oil can be
directly used as salad oil because it will normally meet this specification, whereas
other oils, such as sunflower and corn, must be dewaxed before they can meet typi-
cal salad oil specifications. Soybean oil may be partially hydrogenated and then
winterized to achieve greater oxidative stability and still not crystallize nor lose
proper emulsion properties when refrigerated, although most of the soybean oil
used in commercial dressings is not hydrogenated.
New nutrition-oriented salad and cooking oils have been developed in recent
years. LoSatSoy is an oil low in saturated fatty acids that was developed at Iowa
State University, licensed to Pioneer Hybrid International (Johnston, IA), and com-
mercialized as a salad or cooking oil. This specialty soybean oil has one-half the
amount of saturated fatty acids in normal soybean oil (7% versus 15%); therefore, it
is promoted as having improved nutritional and health benefits.
Other specialty soybean oils, low (<2% or <1%) in linolenate and with
improved oxidative stabilities in salad and cooking oil applications, are comparable
with typical soybean oil that is partially hydrogenated. Today, low-linolenic-acid
soybean oil is an attractive alternative to hydrogenated oil that contains trans-fatty
acids. Beginning in 2006, labeled food products must disclose both the grams of saturated
fat and grams of trans-fat per serving (232). This is inducing food companies to
eliminate or significantly reduce trans-fatty acid contents of their products.
All specialty soybean oils require identity-preserved soybean production, crush-
ing, and refining systems. As financial incentives are needed all along the produc-
tion process to compensate for increased costs of identity preservation, specialty
soybean oils command premium consumer prices and have been slow to impact
soybean oil markets.
618 SOYBEAN OIL
TABLE 17. Trading Specifications for Soybean Cooking and Salad Oils (229).
a
Typically a refined, bleached, and deodorized oil.
b
Refined, bleached, partially hydrogenated, winterized, and deodorized, pure soybean oil.
c
Analyses in accordance with the Official and Tentative Methods of the American Oil Chemist’s Society
Champaign, Illinois, unless indicated otherwise.
d
Federal specifications No. JJJ-S-30G dated March 24, 1978, issued by U.S. General Services Administration,
Washington, D.C.
e
The salad oil may contain properly refined and deodorized cottonseed, corn, peanut, soybean, sesame,
sunflower, or safflower vegetable oils or a mixture of these oils. Olive oil shall not be used. Edible vegetable
oils not specified may also be used provided they are in accordance with good commercial practice.
f
Specifications per announcement PV-50–1 dated June 17, 1976, issued by Agricultural Stabilization and
Conservation Service, U.S. Department of Agriculture, Shawnee Mission, Kansas.
g
0.05% will be acceptable if propyl gallate has been added as an antioxidant or as a component in an
antioxidant.
h
Determination will be made within 7 days after packaging each lot.
i
Active oxygen method.
j
Exclusive of particles of resinous flux material from can manufacture.
k
Association of Official Analytical Chemists’ Method No. 28.107.
l
The oil after heating shall be bland and free from beany, rancid, painty, musty, soapy, fishy, metallic, and other
undesirable or foreign flavors and odors when tested by the method prescribed in footnote m within 7 days
after packaging each lot.
m
Approximately 50 g of the finished product shall be placed in a clean 150-mL Pyrex glass beaker and heated
to a temperature 177 ! 3% C. The oil shall be examined for odor at this temperature, and for flavor, each
cooling to approximately 38% C. From Federal Specification JJJ-S-30G.
n
Heavy metal scavengers, antifoaming agents, and antioxidant materials may be added to improve the
keeping quality and use performance of the oils. The ASCA specifications also permit the addition of
oxystearin. Such additives should be of a kind and at levels permitted in edible oil products under the federal
Food, Drug, and Cosmetic Act and regulations promulgated thereunder.
o
Preservatives ‘‘generally recognized as safe’’ are permitted.
p
During the cooling stage of deodorization, 0.005% of citric acid or 0.006% of monoisopropyl citrate shall be
added to the oil.
q
The packaging gas shall be of food-grade quality and may consist of pure nitrogen or a mixture of nitrogen
and approximately 10% of carbon dioxide plus other inert gases in the atmosphere, but it shall contain no
more than 0.005% oxygen. Maximum permissible oxygen content of the headspace gas within 15 min after
the oil is packaged is 0.50% as measured at standard temperature and pressure. Measurement shall be made
at time of packaging or within 15 min thereafter. For method of analysis, see Bulletin 916, issued in 1963 by
American Dry Milk Institute, Chicago, IL.
fats are heated in the presence of moisture, as often is the case in food applications,
fatty acids are released via hydrolysis of the ester linkages (233). The free fatty
acids, in turn, can accelerate oxidation of the oil. Decomposition and condensation
of hydroperoxides also produces a multitude of nonvolatile monomeric products,
including di- and tri-oxygenated esters, and dimeric and polymeric materials, espe-
cially at elevated temperature. Many of these dimers and polymers are known to be
rich sources of volatile carbonyl compounds and decrease the flavor and oxidative
stability of soybean oil (234). These high-molecular-weight materials also can pro-
duce a series of physical and chemical changes to the oil and food products, includ-
ing increased viscosity, polarity, free-fatty acid content, development of dark color,
and an increased tendency of the oil to foam (233).
A typical soybean oil shortening is generally hydrogenated to enhance its
stability, making it suitable for frying procedures. In addition, polydimethylsiloxane
is routinely added at a level of 0.02–2 ppm as an antifoaming agent, which greatly
extends the frying life of soybean oil (235). The antioxidants mentioned in the
subsection on Cooking and Salad Oils provide oil stability prior to frying and
can enhance the oxidative stability of the fried food. Even though most antioxidants
are volatile at frying temperatures, with their concentration decreasing during
frying, some antioxidant is transferred to and retained in the food (carry through),
thus providing antioxidant protection in the food during storage. In tests,
heated palm olein with no frying lost 70% of its original BHT and 60% of the
original BHA after 8 hr (236). TBHQ being the highest molecular weight (lowest
volatility) of the typical antioxidnts, provides the greatest carry-through benefit
(237).
Extensive hydrogenation produces flaked fats or shortening-like products for fry-
ing applications, which offer convenience in filling fryers and excellent frying sta-
bility. Unfortunately, the process of hydrogenation creates trans-fatty acids as
byproducts of the reaction As noted elsewhere in this chapter, recent concerns about
the presence of trans-fatty acids in our diets, and the subsequent new labeling
requirements for trans-fatty acids (232), have prompted food manufacturers and
oil producers to explore alternative treatments to create soybean oil that is stable
to frying.
One procedure to increase stability without creating trans-fatty acids involves
adding a small amount of a fully hydrogenated oil (hardstock) to a typical soybean
oil. The blended oil is then interesterified to create a stable frying oil without
trans-fatty acids. In a recent study, the low-linolenate soybean oil noted in the
subsection on Cooking and Salad Oils, when blended with 5% of a soybean oil
hardstock, was as stable as a traditional trans-fat-containing soybean oil that
had been stabilized for deep-fat frying, while still retaining excellent flavor
characteristics (238). Another approach to enhance frying stability of soybean
oils is to increase the oleate concentration in the soybean oil created by the
plant, either through traditional plant breeding or biotechnological methods. The
resulting oil, however, when used in frying, creates a fried food with a stale,
waxy-like flavor that lacks the desirable flavor components typical of a fried
food (239, 240).
FOOD AND BIOBASED PRODUCT USES OF SOYBEAN 621
In the United States, mayonnaise, salad dressing, and French dressing are defined
by Standards of Identity issued by the U.S. Food and Drug Administration (FDA;
Code of Federal Regulations, Section 21, 169.140) (241). The Food, Drug and Cos-
metic Act of 1930 and later revisions and amendments were promulgated to prevent
adulteration and misrepresentation of certain food products by establishing
Standards of Identity.
Mayonnaise is defined as a semisolid food prepared with not less than 65% vege-
table oil, and egg yolk and vinegar. Most mayonnaise in the United States, however,
contains 75–82% oil, to get the proper texture (242). Soybean oil is usually used in
mayonnaise but winterized cottonseed, corn, and canola and hydrogenated soybean
oil also can be used. Mayonnaise is an oil-in-water emulsion with oil droplets mea-
suring 1–2 mm in diameter. The higher the oil content, the more tightly the oil dro-
plets are packed in the continuous water phase and thus, the greater the viscosity
and rigidity. Mayonnaise production is partly an art because of the difficulty of pro-
ducing an oil-in-water emulsion in which the dispersed phase has seven times more
volume than the continuous phase. The protein in the egg yolk solids is the only
emulsifier allowed and processing conditions play critical roles in achieving
high-quality and high-stability mayonnaise.
Salad dressings are also oil-in-water emulsions and were developed as alterna-
tives to mayonnaise. The Standard of Identity (21 CFR, 1699.150) requires that sal-
ad dressings contain not less than 30% vegetable oil (but most contain 35–50% oil),
vinegar, *4% egg yolk, and starch. For texture and viscosity, salad dressings rely
on starch, in contrast to mayonnaise, which depends on greater oil content. The oils
used in salad dressings are selected using the same criteria for mayonnaise.
The qualities of mayonnaise and salad dressing are determined by the physical
and oxidative stability of its lipid components. Phase separation or emulsion
breakdown is caused by mechanical shock, agitation, extreme temperatures, or
fat crystallization. Oxidation of vegetable oil and egg lipid also can occur. As the
quality of oil plays a major role in the flavor stability of these products, only the
best quality salad oil should be used. It is particularly important to use salad oils
with long cloud point times (high cold test hours). If fat crystals form during storage
at refrigerated temperatures, the emulsion will break and the product will become
unsightly with visible free oil. Crystal inhibitors, such as oxystearine, lecithin, and
polyglycerol esters, are allowed to prevent crystallization and emulsion breakdown.
Although mayonnaise and salad dressings are spoonable products due to their
high viscosity, French dressing is a pourable oil-in-water dressing. French dressing
must contain *35% oil as defined by a Standard of Identity (21 CFR, 169.115). Egg
products are optional. Other dressings, such as Thousand Island, are not subject to
Standards of Identity, and any ingredients can be used. Pourable dressings can be in
two different finished forms; emulsion or two phases depending on whether the pro-
duct is homogenized. The oil used in these products is predominantly soybean salad
oil in the United States. In Canada and Europe, other salad oils are often used,
depending on the availability and costs of those vegetable oils in each specific region.
622 SOYBEAN OIL
As the oil contents of mayonnaise, salad dressings, and French dressing are high,
it is important to prepare them from salad oils that taste bland and are relatively
stable to oxidation. Peroxide values of the oil should be <2 meq/kg. Even early
stages of oxidation can be detected in mayonnaise and salad dressings as ‘‘grassy’’
and ‘‘beany’’ flavors. Packaging with an inert headspace is important to prevent
oxidation during distribution, retailing, and consumer storage. Storage under refrig-
eration is important once the package is opened and the headspace gas becomes
replaced with air.
11.6. Margarine
Margarine was first produced in 1869 by the French chemist Hippolyte Megge
Mouries. During the Franco-Prussian War, he was awarded a prize and patent for
his invention of a butter substitute. It was not until the 1940s, however, that mar-
garine became widely used. Until then, the powerful dairy industry in the United
States prevented the sale of colored margarine in many states, and consumers did
not readily accept white table margarine. Today, more than twice as much margar-
ine is consumed as butter per capita in the United States, and margarine is no longer
considered a cheap imitation of butter. Unlike butter, margarine can be formulated
from a variety of fats and oils to give a variety of physical and functional properties,
which are needed in many food applications today.
In the United States, margarine or oleomargarine is also controlled by an FDA
Standard of Identity (21 CFR, 166.110), requiring at least 80% fat. Soybean oil is
predominantly used in the United States, followed by cottonseed and corn oils. The
other 20% of the margarine formulation may be made up of water and other
optional ingredients, including milk products, soy protein isolate, salt, selected
emulsifiers (up to 0.5%), mold inhibitors, antioxidants, color additives, flavorings,
and acidulants. Margarine is a water-in-oil emulsion.
The traditional retail form of margarine is stick margarine, but margarine is now
also marketed as pourable and soft tub products. Margarine may also be sold as a
whipped product in which air or an inert gas is incorporated. Still other margarine-
like forms, including polyunsaturated and low-fat spreads, have been developed to
satisfy consumer demands for improved convenience and reduced saturated fat and
calories. In addition to the traditional use as a table food, margarine is also widely
used in baking applications such as in cookies and as roll-in fats for puff and Danish
pastries.
A significant recent consumer trend is increased demand for margarine-like
spreads that are not controlled by a Standard of Identity and that contain much
less fat. Most spreads contain 40–60% fat with 40% fat spreads being more popular
in Europe and 60% in the United States. During the past 15 years, however, very
low-fat spreads containing less than 20% fat have been introduced. As a result of
these trends, there are significantly fewer 80%-fat margarine products available in
the United States today than in the previous decades. Stabilizing these high levels of
aqueous phases in such a small amount of fat as the continuous phase requires spe-
cial equipment to generate the necessary shear and higher amounts of emulsifiers.
FOOD AND BIOBASED PRODUCT USES OF SOYBEAN 623
Moustafa (243) reports that the aqueous droplets must no longer be spherical but
rather polyhedral when loading levels of the aqueous phase exceed 74%.
Margarine processing includes blending the fats separately from the aqueous
phase ingredients and water, dispersing and emulsifying the aqueous phase within
the fat phase, chilling to solidify the fats, pin working the solidified mass, resting,
forming, and packaging. The ingredients are emulsified before being fed into a
swept-surface heat exchanger for crystallizing. The mass emerging from the cool-
ing tubes is partially solidified, and it is further crystallized in the working unit. The
texture of the product is further modified in the resting tube before the margarine is
packaged.
Margarine and shortening have fat crystal networks in which liquid oil is
entrained. As a result, they exhibit a yield stress that must be exceeded before
the product begins to flow as a viscous fluid. The yield stress is related to spread-
ability. The rheological properties of margarine have been discussed by Segura
et al. (244).
In North America, margarines may be composed of blends of hydrogenated soy-
bean oil and palm oil, partially hydrogenated soybean oil and cottonseed oil, liquid
soybean oil and partially hydrogenated soybean oil, liquid corn oil and hydroge-
nated corn oil, or simply hydrogenated soybean oil. Most oil blends contain high
levels of soybean oil to keep costs competitive. Table 18 shows some typical com-
positions and properties of margarine.
The most important functional properties of margarines and spreads are spread-
ability and hardness, oiliness, and melting characteristics. These properties relate to
fat level, proportion of solid fat, fat melting point, and crystal form. Diverse tex-
tures and functionalities can be achieved by varying the extent of hydrogenation.
Consistency and emulsion stability depend on the amount and type of crystallized
fat. Spreadability and hardness can be predicted by the solid fat index and penetra-
tion measurements. A cone penetrometer is typically used to determine margarine
hardness (245). Typical margarines should be spreadable at refrigeration tempera-
tures, remain semisolid at ambient temperatures, and melt at less than body
temperature. Oil-off refers to the separation of liquid fat when the fat crystals no
longer form a network able to hold the liquid oil.
Melting Point
———————— ——————— Trans IV
Soybean Oil Type 10% C 21.1% C 33.3% C (% C) (%) (calc)
Fats exhibit polymorphism in which they can exist in different crystalline forms
depending on how the triacylglycerols pack in the crystal and a, b0 , and b poly-
morphs are known. The preferred polymorphic form for margarine is b0 , which
gives a smooth, pleasing mouthfeel and proper spreadability. Despite hydrogenated
soybean oil’s tendency to form b crystals, it is used in over 90% of all margarines
and table spreads in the United States. The less heterogeneous the fatty acid com-
position of the hydrogenated fats, the more it is b tending. Hydrogenated fats richer
in trans-isomers are less b tending and tend to produce margarines with smoother
textures. Blending small amounts of b0 -tending base fats (palm and cottonseed
oils) or different soybean base oils increase fatty acid heterogeneity favoring b0
crystal stability. Blending unmodified oils with oils that have been hydrogenated
to various degrees allows the production of margarines with desirable texture.
The greater the number of base stocks available, the greater the flexibility to pro-
duce a wide range of products and the higher the tolerance to processing conditions.
Different procedures for designing good margarine from various base stocks were
evaluated by Cho et al. (246).
Base oils for margarine must be hydrogenated to achieve the desired solid-fat
content with the consequential isomerization of some fatty acids. The new regula-
tions requiring reporting of trans-fats content on labels may dissuade some consu-
mers from using traditional margarine. Emken (247) reported that some traditional
margarines may have as much as 21% trans-fatty acids while Kellens (187) found
as much as 31%, and D’Souza et al. (248) reported that the high-melting acylgly-
cerols contained in hydrogenated base stocks used for formulating North American
margarines have 33.1–45.0% trans-fatty acid content in stick margarine and 22.4–
30.1% trans-fatty acid content in soft margarine. Trans-acyl groups contribute to
the firmness of margarine. A recent comprehensive review concluded that consum-
ing more than 4% of total calories as trans-fatty acids may raise plasma lipid levels
(249) and may cause heart disease (250, 251).
Some companies are producing low-trans- or zero trans-margarines by random
(252) or directed interesterification of mixtures of unhydrogenated and fully hydro-
genated soybean oils and other fats (253). To produce these products, a liquid oil
and completely hydrogenated hardstock are interesterified, so that proper plasticity
can be obtained. Oils that contain considerable amounts of palmitic acid favorably
influence crystallization and polymorphic form of the interesterified fat blends
(254).
Chemical interesterification is conveniently achieved by using alkali metal
methylates as a catalyst. Microbial lipases are also used as biocatalysts in enzy-
matic interesterification. In contrast to the chemical process, the enzymatic process
can be more selective if an enzyme with positional specificity is used, but this
reaction is usually much slower and more sensitive to reaction conditions. Recent
developments in lipase-catalyzed interesterification have resulted in new industrial
applications of this process (255). Nevertheless, the high costs of enzymes and pro-
cess equipment may limit widespread adoption of this process.
In developing trans-free fat, various methods for laboratory-scale, pilot plant,
and commercial batch reaction were described by Erickson (256). List et al.
FOOD AND BIOBASED PRODUCT USES OF SOYBEAN 625
11.7. Shortenings
Shortenings are fats of vegetable or animal origin used in baking, but the term
shortening also has been accepted as a term to describe semisolid fats for frying
and cooking. Just as in margarine, the solid fat exists as a tight network of small
crystals, which trap liquid oil. Plastic shortenings differ from margarine in that
shortening is not an emulsion; it is all lipid material and may contain emulsifiers.
Prior to the development of hydrogenation, lard and tallow were the principle short-
ening fats, but these fats lack the diversity of texture and functionality required for
many products. Today, most shortenings contain at least some soybean oil, largely
because it is the least expensive oil that can confer adequate functionality. Short-
ening is available in many forms: plastic and semisolid (cubed, sheeted, and
printed), pourable fluid (with suspended solids), encapsulated powder, and flaked.
Most plastic shortenings are produced by blending oils with hydrogenated fats and
often emulsifiers and solidifying or crystallizing and plasticizing the blend. The
shortening is packaged and tempered by holding it in a quiescent state for several
days at 30% C. During solidification, 10–25% air is often incorporated to improve the
color and texture. Pourable and fluid shortenings are produced by blending appro-
priate oils and emulsifiers. They are crystallized by cooling the fluid mass and stir-
ring the suspended crystals for 4–6 hr at precise temperatures so that large crystals
do not develop, and the fluid becomes stabilized.
Shortenings are added to baked goods to shorten or tenderize them by interrupt-
ing the gluten structure. Shortenings improve mouthfeel and eating qualities, add
lubricity, improve dough-handling properties, contribute flavor and structure, and
promote desirable crumb grain and texture (261). Shortening and tenderizing
effects are especially important in cakes, piecrusts, pastries, cookies, and crackers.
Generally, solid fat indices that change little with temperature are desired for most
shortening applications. Table 20 shows plasticity and melting properties of differ-
ent commercial shortenings. Typical shortening levels are 2–5% in bread, 5–25% in
cake, 20–30% in sweet goods, 30–40% in puff pastry, and 20–35% in piecrusts.
Many plastic shortenings are packaged in 50-lb polyethylene-lined boxes, pri-
marily for use in retail bakeries, e.g., in grocery stores. These are difficult to handle
in large, automated wholesale bakeries. Sometimes, 190-kg drums are used, but are
still difficult to manage and use in the bakery where large amounts are needed.
Pourable and pumpable fluid shortenings were developed to avoid these problems
and are based on soybean oil. However, liquid oils do not cream and aerate well.
The addition of small amounts of hardfats, known as stearine, and various emulsi-
fiers can impart good functional properties to the liquid shortening.
Although adequate quality bread and rolls can be produced without shortening
by using the sponge-and-dough or straight-dough methods, the inclusion of short-
ening increases volume by as much as 25% compared with breads with no short-
ening. This volume increase often is referred to as oven spring, and it reduces
firmness throughout the products storage life. The largest volume of bread is
made by the continuous-mixing method in the United States and shortening is cri-
tical to good quality bread manufactured when using this method. Shortening
TABLE 20. Typical Compositions and Properties of Baking Shortenings.
Cookie and pie dough shortening Partially hydrogenated soybean and palm oils 26–30 18–22 16–20 12–15 9.5–13 46–48
(unemulsified)
Cake and icing shortening Partially hydrogenated soybean and cottonseed oils 23–27 16–19 15–18 12–15 9–12 48–50
(mono and diglycerides)
Yeast-raised sweet goods Partially hydrogenated soybean and palm oils (mono and 24–29 14–18 9–12 44–47
diglycerides)
Fluid cake shortening Partially hydrogenated soybean oil (mono and diglycer-
ides, triglycerol monostearate, sodium stearoyl 2-
lactylate)
High volume cream filling and Partially hydrogenated soybean and palm oils (mono and 25–28 19–22 18–21 14–17 11–14 47–49
icing diglycerides, polysorbate 60)
Biscuit shortening Partially hydrogenated soybean and palm oils 25–30 16–20 7.5– 44–47
(unemulsified) 11.5
Roll-in margarine for yeast-raised Partially hydrogenated soybean and palm oils (mono and 25–30 15–19 6–9 41–42
sweet goods diglycerides)
Fluid bread shortening Partially hydrogenated soybean oil (mono and
diglycerides)
Fluid bread shortening Partially hydrogenated soybean oil (mono and
diglycerides, sodium stearoyl 2-lactylate, ethoxylated
mono and diglycerides)
628 SOYBEAN OIL
delays starch gelatinization and allows the dough to expand more before the struc-
ture is set. Maximum loaf volume, which is a desirable trait in the United States, is
achieved with 6% of emulsified shortening, based on flour weight, but, in practice,
3–5% is normally used. Hardfats in bread shortenings are important in reducing col-
lapse of the loaf’s sidewall. At least 4% hydrogenated lard stearine is desired in
many bread shortenings. Refined, bleached, and deodorized soybean oil is used
in most commercial white pan breads.
Bread shortenings should crystallize in the b form. The base fat of a typical plas-
tic bread shortening is comprised of 90% partially hydrogenated soybean oil (70
IV) and 10% lard stearine (<5 IV); whereas the base fat of a typical fluid bread
shortening is comprised of 95% partially hydrogenated soybean oil (95 IV) and
5% lard stearine. Mono-and diglycerols, are added to reduce staling rate and
more functional emulsifiers, such as sodium steroyl-2-lactylate or ethoxylated or
succinylated mono-and diglycerols, are added as dough conditioners to impart
greater mixing tolerance to enable the bread to withstand abuse without loss of
loaf volume (262).
Using emulsified shortening in layer cakes, cake doughnuts, and muffins
increases volume and reduces air cell size and produces a fine internal grain.
Creaming is defined as the mixing of the shortening over wheat flour particles
and incorporating of air nuclei into the fat. The air nuclei can become sites for
gas bubble formation, which is important in cakemaking. The large number of min-
ute air bubbles incorporated into shortening improves the leavening in baked goods.
For the shortening used in cakes and icings, small ('1 mm) needle-like b0 crystals
are preferred to the larger (5–15 mm) b crystals because the b0 shortenings appear
smooth, provide good aeration, and have better creaming properties (263).
Typically, partially hydrogenated soybean oil is blended with cottonseed or palm
oil hardstock to obtain b0 crystals. Most cake shortenings contain mono- and digly-
cerides to decrease the size of entrained air cells during creaming, to produce finer
air cells and grain in the cake crumb, and obtain a larger volume per unit weight of
batter (specific volume). To achieve proper aeration of fluid cake shortenings, how-
ever, partially hydrogenated soybean oil with b-tending soybean hardstock is
balanced with a-tending emulsifiers, which are typically mono- and di-glycerides
and glyceryl-lacto fatty esters.
Generally, plastic baking shortenings should be firm and plastic, but not brittle or
too soft and oily. Hardfat is added to soybean oil to achieve proper texture, plasti-
city, and creaming properties. Plastic shortenings should be soft and plastic at low
temperatures and still remain semisolid at body temperature.
Soybean oil is excellent for preparing hydrogenated base stocks from which a
wide array of shortenings is made. Up to 50% soybean hardfats are blended with
partially hydrogenated soybean oil in some shortenings. Soybean hardfats, however,
crystallize in the b polymorph unless blended with an equal or greater amount of b0
hardfat, such as hydrogenated palm or cottonseed oil. Partial hydrogenation of the
base soybean oil improves the oxidative stability of the shortening. The amount of
hardstock is varied to achieve the desired texture for the specific product applica-
tion. Various kinds of baked goods need varied shortening functionalities and
OXIDATIVE QUALITY OF SOYBEAN OIL 629
that result can decompose to yield free radicals, and the reaction mode quickly
becomes autocatalytic in the presence of triplet oxygen. A study by Carlsson et
al. (283) found that the photo-oxidation of various unsaturated vegetable oils was
not retarded by known free-radical scavengers, but was retarded by compounds
known to quench singlet oxygen. Furthermore, the degree of retardation apparently
paralleled the singlet oxygen-quenching ability of these compounds.
Commonly, the fatty acids in food lipids are exposed to heat during oil
processing and food manufacture. Once peroxides are formed, they can decompose
and generate free radicals, and the rate of peroxide decomposition increases with
temperature. Such reactions are of extreme importance to both consumers and
processors, because of their flavor significance, and under frying conditions
they can affect the physical, nutritional, and toxological properties of the fried
food.
Enzymes native to plants and animals can initiate oxidation reactions. The most
important and best known of these enzymes is lipoxygenase (linoleate:oxygen oxi-
doreductase, E.C. 1.13.11.12) (LOX) (284, 285). Enzymatic oxidations in plant sys-
tems are mediated by lipoxygenases that use molecular oxygen to catalyze the
oxidation of lipids containing a cis, cis-1,4-pentadiene moiety, such as linoleate
and linolenate. The reaction leads to the formation of hydroperoxides, giving the
same isomers as those formed during autoxidation of linoleate and linolenate. Soy-
beans are a rich source of lipoxygenase isozymes known as LOX-1, LOX-2, and
LOX-3, and their activity is associated with the development of off-flavors, espe-
cially green-beany flavors, in soybean products (285).
Monohydroperoxides are the primary products of lipid oxidation. A variety of
hydroperoxides with positional and geometrical isomers are formed depending
on the position and number of double bonds of the unsaturated fatty acids and
the oxidation mechanism. A number of reviews have been published on the com-
position of isomeric hydroperoxides formed from oxidation of oleate, linoleate, and
linolenate (286, 287–291). The hydroperoxides formed are odorless, but they are
relatively unstable and are the precursors of a variety of volatile and nonvolatile
scission products that are important to the oxidized flavor.
Secondary volatile scission products from primary hydroperoxide decomposition
include aldehydes, alkanes, alkenes, alkynes, alcohols, and hydrocarbons. There are
considerable differences, however, in the flavor significance of these volatile com-
pounds. When estimating the impact of volatile oxidation products on flavor, it is
necessary to know not only their relative concentration, but also their relative
threshold values. One way of evaluating flavor impact is to divide the concentration
by the threshold concentration, although the relative flavor impact may change with
absolute concentration (292). Also, interactions among flavor compounds in the
olfactory response may be important. The relative volatility also may play a role
if a compound must be in the gas phase to reach the olfactory organ. Lee et al.
(293) created equations to relate the flavor impact of individual volatiles, dispersed
in an oil-water emulsion, to a specific concentration of 2-heptanone (Table 21). By
this method, in a fresh and oxidized soybean oil, nonanal contributed the greatest
individual effect on the flavor intensity, followed by trans, trans- and trans,
632 SOYBEAN OIL
Day
—————————————————
—————————————
Component 0 4 7 11
The phenolic antioxidants achieve stability by forming resonance hybrids (Figure 10)
(297). A radical intermediate, such as semiquinone, can undergo a variety of
reactions, including dismutation, to form a stable quinone and can regenerate the
original hydroquinone (Figure 11). However, these antioxidants generally lose their
efficiency at elevated temperatures, and they are most effective during the induction
period. Once the antioxidant is consumed, oxidation accelerates (297).
Preventive antioxidants reduce the rate of the chain initiation. The most impor-
tant initiation suppressors are metal deactivators that chelate metal ions. Metal
deactivators used for stabilizing edible fat and lipid-containing foods include citric,
phosphoric, tartaric acids, and phospholipids. Peroxide destroyers also are preventive
OH O O O
ROO + ROOH +
OH O OH OH
O O OH O
+ +
OH OH OH O
various chemical tests, however, can be used to predict the sensory quality of fin-
ished oil products.
Peroxide value, expressed as milliequivalents of peroxide per kilogram of oil,
measures the primary oxidation products of oils—the hydroperoxides. The peroxide
value has shown a particularly good correlation with sensory flavor scores of soy-
bean oil, and its use during storage is quite common. The peroxide value is an index
to the oxidative state of an oil. Soybean oil is considered ‘‘fresh’’ with a peroxide
value <1.0 mEq/kg, to have low oxidation with 1.0–5.0 mEq/kg, to have moderate
oxidation at 5.0–10.0 mEq/kg, to have high oxidation at >10.0 mEq/kg, and to have
poor flavor quality at >20 mEq/kg (6). Several methods (300–303) can be used to
measure the peroxide value of an oil depending on the specific circumstance.
One of the first steps in the oxidation of polyunsaturated fatty acids is a shift in
the position of double bonds, resulting in the formation of conjugated hydroperox-
ides. The conjugated structure absorbs strongly at a wavelength of 232–234 nm.
The conjugated diene value (300) is expressed as the percentage of conjugated die-
noic acid in the oil and is an indication of initial or primary oxidation products.
Conjugated diene value can be used as a comparative method only when the oils
have the same initial fatty acid composition, because the greater the amount of
polyenoates in an oil, the greater the potential rise in the conjugated diene value.
As a result, this method should be used as a relative measurement of oxidation in an
oil only if the fatty acid composition is known (303).
As aldehydes and some ketones have long been identified as oxidation and
breakdown products of fats, their determination also has been common in soybean
oil quality control. The p-anisidine value (300) measures light absorbance of alde-
hydes, primarily 2-alkenals, and 2,4-dienals at 350 nm. However, this measure is
not entirely specific, because the color intensity developed depends not only on
the concentration but also on the structure of the aldehyde. Therefore, the results
are comparable only within oils of similar type and treatment (304).
Free fatty acid (305), polar compounds (300), viscosity, and color analyses are
often performed to determine the degree of abuse that oils receive during heating or
frying. They are important indicators of frying oil quality, because these compo-
nents affect the quality of the fried food. The free fatty acid increase during frying
indicates released from triacylglyceride ester linkages via hydrolysis (233). Thus, it
is an important marker for oil quality. Abused frying oil should be discarded if it
contains >27% total polar compounds, according to a German standard of frying
oil quality (306). Changes in viscosity and color of the frying oil also are used as
indicators of the extent of frying oil degradation.
There are many other methods for measuring lipid oxidation and quality by che-
mical means. Among the best-known procedures are the thiobarbituric acid (TBA)
test, carbonyl value, and headspace oxygen analysis. These methods have been
reviewed and discussed elsewhere (287, 307).
The volatile carbonyl compounds formed during oxidation of fats and oils are
major contributors to off-flavor development. Therefore, there have been significant
efforts at identifying and quantifying these compounds. It is difficult to analyze
these compounds in fats and oils for several reasons. First, it is difficult to remove
636 SOYBEAN OIL
them quantitatively from the fats and oils. Second, widespread contamination by
carbonyls in solvents, glassware, and other laboratory materials may cause artifacts.
Finally, hundreds of volatile compounds may be formed in fats and oils during oxi-
dation causing difficulties in the interpretation. Today, the use of efficient gas chro-
matography (GC) columns and proper means of identification has made reliable
volatile compound analysis become possible.
Three basic GC procedures are generally employed (300), including static head-
space, dynamic headspace, and direct injection. Static headspace involves equili-
bration of gases from the area above a liquid sample; a set volume of the
headspace gas from the sample is then injected directly into the GC for separation
and quantification. The dynamic headspace method, also known as purge and trap,
employs a sorbent, such as Tenax GC, Chromosorb, or Porapak Q, to collect vola-
tile compounds that are swept from a heated sample with an inert gas such as
helium or nitrogen. After trapping, the sorbent may be extracted with solvent, or
transferred directly to the GC inlet port. In direct injection, an oil sample may be
injected directly into the port of the GC through a silanized glass wool plug. Each
of these methods has their own advantages and disadvantages (287).
Recently, the method of gas chromatographic solid-phase microextraction (GC-
SPME) has been developed (308–310). This method uses fibers coated with various
polymers to extract volatile compounds from a food system. The method can be
used in solid, liquid, and gaseous systems. It is fairly easy to evaluate volatile com-
pounds by this analysis and to maintain consistent conditions.
Evans et al. (311) and Scholz and Ptak (312) used GC analysis of n-pentane as a
measurement of rancidity of vegetable oils. Dupuy et al. (313, 314) determined the
volatile carbonyl compounds from soybean oil using a modified gas chromato-
graphic inlet tube and found good correlations between the volatile profile analysis
and sensory scores. The Flavor Quality and Stability Committee of the AOCS eval-
uated GC volatile profiling as a standard method of flavor evaluation (275). As a
result, they wrote two Recommended Practices, entitled ‘‘Volatiles in Fats and
Oils by Gas-Liquid Chromatography’’ Cg 4-94, 1997 (300) and ‘‘Correlation of
Oil Volatiles with Flavor Scores of Edible Oils’’ AOCS method Cg 1-83, 1997
(300). These AOCS methods were validated in an AOCS collaborative study on
sensory and volatile analyses, in which three methods of volatile compound ana-
lyses were compared with sensory analyses by using the AOCS flavor scales
(315). Despite agreement on the usefulness of these methods, the committee
stressed that only humans can measure flavor, thus these volatile GC methods mea-
sured features such as oxidative stability and compound breakdown—not sensory
perceptions per se.
Not surprisingly, heat treatment, such as commercial and household frying,
accelerates autoxidation. In addition to undergoing autoxidation, when fats are
heated in the presence of moisture, as often is the case in food applications, fatty
acids are released via hydrolysis of the ester linkages (233). The free fatty acids can
accelerate oxidation of the oil. During heat treatment, the formation of dimeric and
cyclic compounds seems to be the predominant thermolytic reaction of unsaturated
fatty acids. In the presence of oxygen during heat treatment, however, oxidative
OXIDATIVE QUALITY OF SOYBEAN OIL 637
polymerization also can occur (233). Obviously, temperature, heating time, avail-
ability of oxygen, etc. can largely influence the extent to which these thermal and
oxidative polymerization reactions occur.
Decomposition and condensation of hydroperoxides also produces a multitude
of nonvolatile monomeric products, including di- and tri-oxygenated esters, and
dimeric and polymeric materials, especially at elevated temperature. Many of these
dimers and polymers are known to be rich sources of volatile carbonyl compounds
and to decrease the flavor and oxidative stability of soybean oil (316). These high-
molecular-weight materials also can produce a series of physical and chemical
changes to the oil and food products, including increased viscosity, polarity, free
acid content, development of dark color, and an increased tendency of the oil to
foam (233).
meet a Lovibond color level of 6.0. Frost-damaged oils often will not meet this
requirement. Oils from frost-damaged beans tend to have an undesirable green col-
or in the crude oils caused by compounds related to, but not identical to, chlorophyll
(includes pheophytin) or some of its derivatives, according to Stern and Grossman
(319). When bleaching such oils, acid-activated clays are more efficient than neutral
clays and increased amounts of bleaching earth make the removal of the green color
more effective. According to Stern and Grossman (319), pretreatment with charcoal
(0.4–1.0%) at 90% C or treatment of a cold hexane-oil mixture with charcoal is effec-
tive in partly removing the green pigment. When charcoal pretreatment is combined
with additional treatment from sugars and activated bleaching clays, complete
removal of green pigments is possible. Hydrogenation can also be used to remove
green color from soybean oil. According to Beal et al. (175), a green oil (IV 132)
hydrogenated to IV 110 in the presence of 1% copper chromate catalyst was no
longer green after cooling and filtration. However, the use of copper chromate is
not a common practice.
When soybeans are exposed to rain or humid weather in the field, the beans tend
to sprout and decay, and the oil from these beans develops a dark-brown color and
chalky texture (312). Drought stress affects protein and oil content of soybeans but
seldom damages oil quality significantly. According to List (317), off-specification
oils from field-, frost-, heat-, and moisture-damaged soybeans result in high refining
losses during processing, poor refined-bleached color, and lowered flavor and oxi-
dative stability. High refining losses may be partly overcome by use of phosphoric
acid or acetic anhydride degumming. Color problems of oils from damaged beans
may be alleviated, in part, by use of acidic bleaching earths, increased amounts of
bleaching earths, and higher bleaching temperatures. Overall, however, the best
practice for producing high-quality oil is to segregate the bad beans and not include
them in the processing.
In both clinical trials and population studies, polyunsaturated fats in the diet
have been shown to actively lower serum cholesterol levels. Soybean oil is consid-
ered to have good nutritive value mainly because of its high concentration of essen-
tial polyunsaturates. As noted previously, it contains about 55% linoleate and 8%
linolenate, both recognized as essential fatty acids. Ingestion of approximately
1–2% of daily calories as linoleate is widely accepted as the amount needed to
meet the essential fatty acid requirement of rodent species and humans (325).
The physiological effects of linoleate have been well characterized. Various
deficiency symptoms include depressed growth, scaly dermatoses, increased skin
permeability, fatty liver, kidney damage, and impaired reproduction. The 8%
linolenate of soybean oil, makes it not only an excellent source of essential fatty
acids, but also a member of the n-3 fatty acid group (the third carbon atom from
the terminal end of the hydrocarbon chain is involved in a double bond). A number
of health benefits have been associated with the consumption of foods or oils that
contain n-3 fatty acids. These associations originally derived from epidemiological
studies of Eskimos who consumed high levels of n-3 fatty acid from seals and
coldwater fish (326). Compared with Danish counterparts, these Eskimos were
found to have a low incidence of heart disease and immune system diseases,
although a somewhat higher level of hemorrhagic stroke. Still today, large-scale
epidemiological studies suggest that individuals at risk for CHD benefit from the
consumption of plant- and marine-derived n-3 fatty acids (327).
been found in human platelets (337). The 9-cis,12-trans-linoleic acid can be con-
verted to 20:4n-6 containing a trans-double bond. Unfortunately, this trans-isomer
of 20:4n-6 inhibited the formation of prostaglandins from all-cis-20:4n-6 (338).
Mensink and Katan (250) reported that a diet high in trans-acyl groups raised total
and low/high-density lipoprotein cholesterol ratio compared with a diet high in cis-
acyl groups may be more cholesterolemic than saturates (339), and were linked to
an increased risk of breast cancer development (340).
The estimated trans-acyl group intake by typical U.S. consumers is 11.1–27.6 g/
person/day (341). A comprehensive review concluded that trans-acyl groups con-
sumed at 4.0% or more of total calories may raise plasma lipid levels (342). As a
result of health concerns over the presence of trans-acyl groups in our diet, mod-
ifying fatty acid composition of soybean oil to improve its oxidative and flavor
stability in ways similar to that obtained by hydrogenation, but without trans-
formation, has become an objective of plant breeders.
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