Reprinted from THE JOCRNAL Of THE A:,lERICAN OIL CHF'.IISTS· SOCIETY. Vo1.58. No.1.

Pages:51A-54A (1981)

4755
Purchased 'by U. S. Dept. ot
Agricu1t1.h""e for. Official Use

Chemical and Physical Effects of Processing Fats and Oils 1

T.L. MOUNTS, Northern Regional Research Center, Agricultural Research, Science and
Education Administration, U.S. Department of Agriculture, Peoria, IL 61604

ABSTRACT Composition of Soybean Oil

Soybean oil is processed for a variety of food uses, salad/cooking The typical compositions of crude and refined soybean oils
oil, margarine and shortening. Crude soybean oil is composed are given in Table I (l). The refining process does not affect
mainly of triglycerides but also contains measurable amounts of the fatty acid composition of the glyceride but does essen-
minor constituents that may have beneficial or detrimental effects tially remove phosphatides and free fatty acids and lower
on oil characteristics. The nature of these minor constituents, the contents of some lesser constituents such as the tocoph-
the role they play in oil stability or deterioration and their fate erols, the sterols and squalene (2). Also present in very
during processing are subjects of this review. Iodine value, fatty
small quantities are a number of other materials including
acid composition, solid fat index and congeal point are chemical
and physical characteristics of oil that are affected by the hydro- wa..-xes, pigments and minerals. Waxes are the esters of long
genation process. Techniques and effects of degumming, alkali chain fatty alcohols and acids that originate from seed
refining, bleaching, hydrogenation, winterization and deodoriza- coats. Although waxes are a minor consideration with soy-
tion are discussed. Utilization or disposal of by-products or wastes bean oil, other oils such as sunflower seed, corn, safflower
from each processing step is reviewed. and sesame contain sufficient amounts of waxes (0.2-3.0%)
to require their removal by a special dewaxing (3). One of
INTRODUCTION the more prevalent pigments is ~-carotene, which is the
most important of the provitamins A. When present in
In many countries, the major edible oils traditionally are higher concentration, ~-carotene is also responsible for the
consumed in a clean but unrefined form. Apart from hy- red color of palm oil. Hydrogenation and high-temperature
drolvsis, which releases free fattV acids, and oxidation, deodorization destroy the chromophore groups of (3-
whi~h causes rancidity, these oils' are unaltered and any carotene. Chlorophyll is also present and gives a greenish
materials naturally present remain in the product. Examples cast to soYbean oil after the removal of the vellow color of
of vegetable oils that are consumed in the unrefined state ~-caroten; during hydrogenation. If immature or freeze-
are p~anut, coconut, rapeseed, mustard seed, palm, olive damaged soybeans are used for oil extraction, the content
and sesame seed oils. However, processing crude oils to of chlorophyll can be sufficient to cause color problems in
finished edible food products is practiced worldwide and producing a finished oil (4). IV1inerais present in trace
is dictated by several factors: (a) consumer preferences, amounts include phosphorus, sodium, iron and copper.
(b) flavor and stability characteristics of particular oils, Iron and copper have been shown to be active catalysts for
and (c) preparation of hardened products from liquid the oxidation of soybean oil (5) and their removal or in-
vegetable oils, i.e., margarines and shortenings. These activation is essentiai for oil stability.
factors have lead to development of technological processes
for treatment of crude oils to make them as bland and PROCESSING
colorless as possible and for modification of the physical
characteristics of the oils. The refining techniques consist The processing techniques employed to produce a finished
of water or acid degumming, alkali refining, bleaching and edible oil from crude oils are outlined in the flowsheet
deodorization. The refined oils and fats may be further shown in Figure 1.
processed by hydrogenation and winterization for different
food uses. Each of these technological processes affects the TABLE I
nature of the oil; the character of these effects forms the
basis of the current discussion. Average Compositions for Crude and Refined Soybean Oil (1)
In the United States soybean oil is the major vegetable
oil used for production of edible food products. Significant Component Crude oil Refined oil
quantities of cottonseed, corn, peanut, safflower and sun-
flower seed oils also are utilized in our domestic marker. In Triglycerides, % 95-97 >99
general, the same technological processes are applied for the Phosphatides, % 1. 5-2. 5 0.003-0.015
Unsaponifiable matter, % 1.6 0.3
refining of all these oils with minor modifications based on Plant sterols, % 0.33 0.13
the characteristics of the particular oil. Therefore, this Tocopherols, % 0.15-0.21 0.11-0.18
paper will be directed to a consideration of processing soy- Hydrocarbons (squalene), % 0.014 0.01 '
bean oil. Free fatty acids, % 0.3-0.7 <0.05
Trace metals
Iron, ppm 1-3 0.1-0.3
1 Presented at Northeast Section, AGCS, Symposium, Newark, Copper, ppm 0.03-0.05 0.02-0.06
N.J., November 5-6,1979.

JAOeS January 1981 /51A

 T.L. MOUNTS

Alkali Refining
Refining of soybean oil is practiced as a purifying treatment
designed to remove free fatty acids, phosphatides and gums,
coloring matter, insoluble matter, settlings and miscella-
neous "unsaponifiable" materials. The treatment has little
effect on the triglycerides of the oil. If crude oil is to be
alkali refined it is conditioned with phosphoric acid to facil-
itate the purifying treatment (8).
Essentiall)T all soybean
,
oil in the United States0 is refined
,
by the continuous process. An amount of 17-18 Be caus-
tic, based on the free fatty acid content of the oil plus a
CAR
WASHING 0.10-0.13% excess, is proportioned into the crude oil and
CAR mixed in a high shear in-line mixer. The soap-oil mixture is
WASHING
heated to 75-80 C and fed to a pressure or hermetic type
I
OEODORIZED
DEODORIZED
OIL
centrifuge for separation into light and heavy density
.Q!1.. phases. Light-phase discharge consists of the refined oil con-
CONVENTIONAL REFINING PHYSICAL REFINING taining traces of moisture and soap; the heavy phase is pri-
marily soap, insoluble material, free caustic, phosphatides
FIG. 1. Processing of edible oils. and a small quantity of neutral oil. Refined oil is washed
with 10-20% by weight of soft water at 90 C. The water-
washing proces~ rem~ves about 90% of the soap content in
Degumming
the refined oil; the remainder of the soap is removed in the
Crude soybean oil is degummed for one or more of the fol- bleaching process (11). Soapstock and wash water are com-
lowing reasons: (a) to produce for export an oil substan- bined and treated with sulfuric acid to convert the soap
tially free of materials that settle out during shipment or into crude fatty acids. Most of the acidulated soapstock is
storage, (b) to recover phosphatides that can be processed used as a high energy ingredient in animal feed. Depending
to make soybean "lecithin" or (c) to remove emulsifying on market demand, acidulated soapstock may be sold to
agents (i.e., phosphatides and mucilaginous gums) that in- fatty acid producers who recover the crude fatty acid by dis-
crease loss of neutral oil when the oil is alkali refined (6). tillation as a valuable by-product of oil refining (12).
Degumming with phosphoric acid has been proposed as a Residue from this distillation is a good source of sterols.
necessary pretreatment to lower the content of phospha- Nelson and Milun (13) reported that the sterol content of
tides and metallic prooxidants sufficiently prior to physical the distillation residue was almost 30%.
refining (i.e., steam refining) of edible oil (7).
Bleaching
The principal method of degumming employed in the
United States is a batch treatment of the oil with 1 to 3% Bleaching of alkali-refined oils removes entrained soaps and
of water, based on oil volume (8). The mixture is agitated reduces color bodies in the oil; it is more appropriately re-
for 30-60 min at 70-80 C. The hydrated phosphatides and ferred to as adsorption treatment. Although batch atmo-
gums can be separated from the oil by settling, filtering or spheric bleaching is still used to some extent in the United
centrifuging. The sludge obtained upon degumming soy- States, batch or continuous vacuum bleaching is generally
bean oil is a mixture of several phosphatides plus an oil practiced. The process consists of agitation of the oil with
carrier and other ingredients (Table II) (9). After drying, 0.5-1.5% acid activated earth at 90-95 C for 15-30 min at
this mixture is marketed as commercial soybean lecithin a vacuum of 26-28 in. Hg followed by filtration to give a
and finds wide application as a wetting and emulsifying clean, clear oil.
agent. Optionally, the lecithin may be bleached before Although bleaching generally improves oil quality with
marketing. About 90% of the phosphatides are removed respect to color, initial and aged flavor, and oxidative sta-
from the oil by water degumming (10). Although most of bility, the technique also has other less obvious effects,
the remaining phosphatides are removed during alkali re- some of which are desirable and others which are undesir-
fining, vegetable oils often contain some phosphatides that able. Four factors have been determined to affect the
are not removed by hydration (5). These phosphatides can degree of bleaching of an oil (14). Adsorption of color pig-
have a deleterious effect on oil quality. European proces- ments by the adsorbent and a reduction in color through
sors use a phosphoric acid treatment of the degummed oil oxidation of certain pigments are two favorable factors.
before alkali refining to facilitate removal of these nonhy- Color increases brought about by oxidation of other pig-
dratable phosphatides. If phosphoric acid is employed, ments and the stabilization of these oxidized pigments
chlorophyll is partially removed from the oil. against adsorption are unfavorable factors. Bleaching earths
were shown to catalyze these oxidation reactions. Vacuum
TABLE II bleaching has mini~ized these unfavorable factors. Such
reaction; and color changes are complex, i.e., oxidation and
Approximate Chemical Composition of Natural Commercial heat can bleach carotenoid compounds; these conditions
Soybean Lecithin (9)
may also encourage the formation of new pigments (15).
Neutral earths and those activated earths that have little
Fraction or no acidity will produce little or no change in the free
fatfY acid (FFA) content of the neutralized oil. Some of
Soybean oil 35 the "more acidic activated earths may add 0.05-0.10% to the
Phosphatidylcholine 16
Phosphatidylethanolamine 14 FF A content, especially if the co~tact time is long or if
Phosphatidylinosi tol 10 moisture or soap is present.
Phytoglycolipids and other minor phosphatides 17 Good soap removal by washing the refined oil before
and constituents bleaching is desirable because the adsorption of relatively
Carbohydrates 7
Moisture 1 large amounts of soap lowers the adsorbent's capacity for
other constituents in the oil. Generally, the soap content

52A / JADeS January 1981

 EFFECTS OF PROCESSING FATS AND OILS

in oil is reduced to 5-10 ppm during bleaching. TABLE III

Conjugation of oxidized polyunsatured fatty acids dur- Commercial Deodorization Conditions (18)
ing bleaching has been reported (16). Oxidation of the oil
before or during bleaching will promote conjugation; there- Absolute pressure 1-6 mm Hg
fore, procedures such as deaerating both initial oil and ad- Deodorization temperature 210-274 C
sorbent and vacuum bleaching help to suppress the conjuga- Holding time at elevated temperature:
tion reaction. trans-Isomerization has been shown to occur Batch type 3-8 hr
Continuous and semicontinuous types 15-120 min
with acid-activated earths, but only at temperatures of 150 Stripping stearn: wt % of oil
C and above, which far exceed those normally employed in Batch type 5~15%
bleaching (17). Continuous and semicontinuous types 1-5%
Product free fatty acid:
Deodorization Feed, including stearn refining 0.05-6%
Deodorized oil 0.02-0.05%
In the edible oil refinery, deodorization is the last process
step used to improve the taste, odor, color and stability of
the oil by the removal of undesirable substances. All com- TABLE IV
mercial deodorization, whether in continuous, semicontin-
uous or batch units, is essentially a steam stripping of the Unsaponifiables in Soybean Deodorizer Distillates (12)
oil for removal of FFA and other volatile compounds.
During the process, peroxide decomposition products, Compound
color bodies and their decomposition products are elimi-
nated and the contents of sterols, sterol esters and tocoph- Tocopherols 12.3
erols are reduced. Conditions of commercial deodorization b. 3.0
(3 and I 7.7
are presented in Table III (18). The goal of deodorization is Q 1.5
to produce a finished oil that has a bland flavor, a maxi- Sterols
mum FFA content of 0.05% and a zero peroxide value. The. Carn pesterol 5.7
modern commercial deodorizer is equipped with a pollution Stigmasterol 5.2
(3-Sitosterol 11.0
control system that consists of three steps: the deodorizer
distillate recovery system, closed circuit condensing water
system and the vapor scrubbing system. The distillate re-
covery system removes 80-90% of the distillate from the genation results in extensive changes in the fatty acids of
steam train before it reaches the condenser. The short-chain the triglycerides, reduces the carotenoid pigments and
fatty acid fractions pass through the recovery unit and are lightens the color.
Commercially, soybean oil hydrogenations are carried
recovered from the vapor scrubbing system. The deodorizer
distillate is a concentrate of tocopherols and sterols and is a out with nickeI cat~lysts; selective hydrogenations under
valuable source of these materials. conditions such as 5-14 psig, 0.05% catalyst at 177 C; and
nonselective hydrogenation under conditions such as 15-50
Tocopherols are natural antioxidants found in vegetable
psig, 0.05% catalyst at 121 C. Saturation of all the unsatu-
oils and contribute significantly to oxidative stability. Due
rated bonds in one triglyceride molecule or in one molecule
to the high tocopherol content of crude oils, they can be
stored for long times if they are protected from air, mois- of fatty acids is rarely the major effect of partial hydrogen-
ation. Shifts of the unsaturated bonds occur both in poly-
ture and high temperature (19). Frankel et al. (20) observed
and monounsaturated acids to yield a wide range of both
that at high concentrations of tocopherol the synergistic
positional and geometric isomers with the same number, or
effect between citric acid and tocopherol was decreased.
fewer unsaturated bonds as the original fatty acids.
The concentration of natural tocopherols in soybean oil
For use as a liquid or salad oil, soybean oil is selectively
was too high for optimum oxidative and flavor stability.
hydrogenated to an iodine value of 115 or less (3). Such
Sterols are complex polycyclic alcohols that are found as a
oils must be winterized to ensure that a clear, liquid oil is
class of compounds in all oils (21). The major sterols in soy-
retained even at lower temperatures. The process involves
bean oil are iJ-sitosterol, campesterol and stigmasterol.
the chilling of the oil to 6 C over a period of 24 hr and
Sterols are used for the production of synthetic hormones,
whereas tocopherols are marketed as vitamin E. Nelson and
Milun (13) determined the sterol and tocopherol contents Commercial Undeodorized Soybean Oil Commercial Deodorized Soybean Oil
of soybean deodorizer distillate by gas chromatographic
18:2w6
analysis (Table IV). 18:3w3
The high temperatures used in the deodorization process 18:3w3
have been shown to cause limited geometric isomerization
of polyunsaturated fatty acids. Using capillary gas chroma- 18:2w6 Artifact
18:1 X
tography, Ackman et al. (22) analyzed the methyl esters
prepared from commercial soybean oils undeodorized and
18:1
deodorized (Fig. 2). They identified two major triene iso-
mers produced by the deodorization: A is cis-9, cis-12,
trans-IS and Cis trans-9, cis-12, cis-IS. Minor amounts of =o Artifact
u
Artifact ...... C
cis-9, trans-12, cis-IS, and trans-9, cis-12, trans-IS were also a: 18:D
identified. 18:D \5o.~."A
The authors suggested that this analysis might be a con- lA "- ~ WU~
venient means of determining if a linolenic-acid-containing Adjusted Retention Tlme--
liquid vegetable oil was subjected to deodorization.
FIG. 2. Comparison of CIS group of acids from soybean oils from
Hydrogenation the same lot of oil before (left) and after (right) ordinary commer-
cial deodorization. Aged butanediolsuccinate polyester open tubu-
Partial hydrogenation of edible oils is practiced to increase lar column operated at 170 C and 40 psig. Elution time ca. 15 min
stability by the selective reduction of linolenic acid. Hydro- for 18:0 (22)_

JAOeS January 1981 I 53A

 T.L MOUNTS

reported in edible oils (24-26). Results of the analysis for

58.4I.V.•~
several of these compounds in raw oils and in oils at various
60- ~ stages of processing is shown in Table V (26). Essentially,
all of the compounds are removed by deodorization. The

'\.
pesticide residues are concentrated in the deodorizer distil-
50 !- late and limit the use of this by-product as a feed additive.

REFERENCES

1. Pryde, E.H., Composition of Soybean Oil, in "Handbook of

Soybean Oil Processing and Utilization," edited by D.R. Erick-
son, E.H. Pryde, O.L. Brekke, T.L. Mounts and R.A Falb,
American Soybean Association, St. Louis, MO, 1980, p. 13-31.
~ 30 f- 2. Gutfinger, T., and A Letan, J. Sci. Food 1\,aric. 25 :1143
(1974).
3. Neumunz, G.M., JAOCS 55(5):369A (1978).
4. List, G.R., C.D. Evans, K. Warner, R.E. Beal, W.F. Kwolek,
L. T. Black and K.J. Moulton, Ibid. 54:8 (1977).
20f- ~ 5. List, G.R., T.L. Mounts and AJ. Heakin, Ibid. 56:883 (1979).
6. Braae, B., Chern. Ind. (London) 36:1152 (1958).
7. Sullivan, F.E., U.S. Patent 2,702,813 (1955).

"" ::::::~>~~
8. Carr, R.A., JAOCS 55:765 (1978).
9. Brekke, O.L., Oil Degumming and Soybean Lecithin, in "Hand-
book of Soybean Oil Processing and Utilization," edited by
D.R. Erickson, E.H. Pryde, O.L. Brekke, T.L. Mounts and R.A
Falb, American Soybean Association, St. Louis, MO, 1980, p.
" , 71-88.
OF. - 50 60 70 80 92 104 10. Meyer, N.W., JAOCS 34:93 (1957).
11. Mounts, T.L., and F.P. Khym, Refining, in "Handbook of Soy-
°C._ 10 21.1 33.3 40 bean Oil Processing Technology," edited by D.R. Erickson,
Temperature E.H. Pryde, O.L. Brekke, T.L. ,""lounts and R.A Falb, Ameri-
can Soybean Association, St. Louis, MO, 1980, p. 89-103.
FIG. 3. Hydrogenation of soybean oil to successively lower iodine 12. Watson, K.S., and M. Hofer, JAOCS 53:437 (1976).
values increases its firmness as indicated by the solid fat index. 13. Nelson, J.P., and AJ. Milun, Ibid. 45:848 (1968).
Hydrogenation conditions: 0.02% nickel catalyst, 15 psig pressure, 14. King, R.R., and F.W. Wharton, Ibid. 26:201 (1949).
300 F (149 C) temperature (23). 15. Swift, G.E., G.E. <'vlann and G.S. Fisher, Ibid. 21 :317 (1944).
16. Mitchell, J.H., Jr., and H.R. Kraybill, JACS 64:988 (1942).
17. Patterson, H.B.W., JAOCS 53:339 (1976).
holding at this temperature for 6 to 8 hr. The high melting 18. Zehnder, C.T., Ibid. 53:364 (1976).
glycerides, palmitic and stearic acid fractions (mainly dipal- 19. Norris, F.A, Handling, Storage and Grading of Oils and Oil
Bearing j\laterials, in "Bailey's Industrial Oil and Fat Prod-
mitoolein and dipalmitolinolein) called soy stearine, crystal- ucts," edited by D. Swern, Interscience Publishers, New York,
lizes and is removed by filtration. The yield of liquid oil is 3rd Edition, p. '601-635.
generally 75-85%. The dewaxing of sunflower oil is accom- 20. Frankel, E.N., P.M. Cooney, H.A. Moser, J.e. Cowan and e.D.
plished by a process very similar to winterization. Evans, Fette Seifen Anstrichm. 61 :1036 (1959).
21. !toh, T., T. Tamura and T. Matsumoto, J AOCS 50: 122 (1973).
Nonselective hydrogenation yields a physically hardened 22. Ackman, R.G., S.N. Hooper and D.L. Hooper, Ibid. 51 :42
product. The degree of hardening is determined by the solid (1974).
fat index (SF!), which is an empirical measure of the solid 23. Latondress, E.G., Shortenings and Margarines: Base Stock
fat content of an oil. While process variables can signifi- Preparation and Formulation, in "Handbook of Soybean Oil
Processing Technology," edited by D.R. Erickson, E.H. Pryde,
cantly affect the slope of the SFr curves, typical SFr curves O.L. Brekke, T.L. Mounts and R.A. Falb, American Soybean
for the hydrogenation of soybean oil are shown in Figure 3 Association, St. Louis, MO, 1980, p. 145-154.
(23). Examination of the SFr curves shows that as the 24. Chaudry, M.M., A.I. Nelson and E.G. Perkins, JAOCS 53:695
(1976).
iodine value end point is decreased, the SFr values at 92 F 25. Hashemy-Tonkabony, S.E., and M.J. Soleimani-Amiri, Ibid.
and 104 F begin to rise rapidly. 53:753 (1976).
26. Chaudry, M.M., A.I. Nelson and E.G. Perkins, Ibid. 55:851
Adventitious Materials (1978).
Residues of chlorinated pesticides are adventitious materials [Received December 26, 1979]

TABLE V

Pesticide Residues in Soybean Oil at Various Stages of Processing a (26)

Deodorized Deodorizer
Pesticide Crude oil Refined oil Bleached oil oil condensate

aBHC 18.0 18.6 10.7 1.2 1459.0

Lindane 8.0 9.1 7.4 178.8
iJ BHC 8.5 7.9 2.3 1.7 173.8
Heptachlor 8.8 14.5 3.2 426.2
Aldrin 10.4 7.6 4.8 0.9 883.8
Heptachlor-epoxide 40.4 59.7 66.5 1.6 3648.4
Dieldrin 222.6 179.2 142.7 8012.9
Endrin 28.3 3.2
OP'DDT 15.4 29.6 1.8 822.7
PP'DDD 8.5 3.2 12.4
PP'DDT 18.8 20.8 12.5 768.2

aparts per billion

54A / JAOeS January 1981