Chapter

4
Edible Oils, Fats,
and Waxes

Mohammad Farhat AIi

4.1 Introduction 86
4.2 Fatty Acids 88
4.3 Glycerides 92
4.4 Physical Properties of Triglycerides 94
4.4.1 Melting point 94
4.4.2 Specific heat 94
4.4.3 Viscosity 94
4.4.4 Density 96
4.4.5 Refractive index 96
4.4.6 Polymorphism 96
4.4.7 Other physical properties 96
4.5 Chemical Properties of Triglycerides 98
4.5.1 Hydrolysis 98
4.5.2 Methanolysis 98
4.5.3 lnteresterlfication 98
4.5.4 Hydrogenation 99
4.5.5 Isomerization 100
4.5.6 Polymerization 100
4.5.7 Autoxidation 100
4.6 Sources of Edible Oils and Main Fats 102
4.7 Oils and Fats: Processing and Refining 103
4.8 Fats and Oils Stability and Antioxidants 115
4.9 Methods of Analysis and Testing of Fats and Oils 118
4.9.1 Identification and compositional analysis 118
4.9.2 Quality control tests 120
References 121
4.1 Introduction
Fats, oils, and waxes are naturally occurring esters of long straight-chain
carboxylic acids. They belong to the saponifiable group of lipids. Lipids
are biologically produced materials that are relatively insoluble in water
but soluble in organic solvents (benzene, chloroform, acetone, ether, and
the like). The saponifiable lipids contain an ester group and react with
hot sodium hydroxide solution undergoing hydrolysis (saponification):
No reaction (unsaponifiable)
no ester group Includes steroids,
prostaglandins,
leukotrienes
Lipids (hot NaOH
solution)

Hydrolysis reaction
(saponifiable)
contains ester group Includes oils,
fats, waxes,
phospholipids

Saponification is a chemical process in which an ester is heated with

aqueous alkali (sodium hydroxide) to form an alcohol and the sodium
salt of the acid corresponding to the ester. The sodium salt formed is
called soap.

Fats and oils are esters of glycerol, the simplest triol (tri-alcohol), in
which each of the three hydroxyl groups has been converted to an ester.
The acid portion of the ester linkage (fatty acids) usually contains an even
number of carbon atoms in an unbranched chain of 12 to 24 carbon atoms.
The triesters of glycerol fats and oils are also known as triglycerides.

Typical fat-triester of glycerol

glycerol

The difference between fats and oils is merely one of melting point:
fats are solid at room temperature (200C) whereas oils are liquids. Both
classes of compounds are triglycerides.
 As glycerol is common to all fats and oils, whether animal or vegetable,
it is the fatty acid part of the fat (oil) that is of interest. The differences
among triglycerides (fats and oils) are because of the length of the hydro-
carbon chains of the acids and the number of position of double bonds
(unsaturation).
The hydrocarbon chains of the fatty acids may be completely saturated
(saturated fat) or may contain one or more double bonds. The geomet-
ric configuration of the double bond in fats and oils is normally cis, If
the chain includes more than one double bond, the fat is called polyun-
saturated. The presence of a double bond puts a kink in the regular zig-
zag arrangement characteristic of saturated carbons. Because of this
kink in the chains, the molecules cannot form a neat, compact lattice and
tend to coil, so unsaturated triglycerides often melt below room tem-
perature and are thus classified as oils.

Unsaturated fat (oil)—includes cis double bond

Kink

Poor packing

Fats and oils are the most concentrated source of energy. They pro-
vide approximately 9 kcal of energy per gram, compared to 4 kcal/g for
proteins and carbohydrates. They are carriers of fat-soluble vitamins and
essential fatty acids. They also contribute to food flavor and mouth-feel
as well as to the sensation of product richness. They are used as frying
fats or cooking oils where their role is to provide a controlled heat-
exchange medium as well as to contribute to color and flavor. They are
also used in many other commercial applications, including soaps, deter-
gents, and emulsifiers, printing inks, protective coatings, and feeds for
domesticated animals.
Waxes are monoesters of long-chain fatty acids, usually containing
24 to 28 carbon atoms, with long-chain fatty primary alcohols. A fatty
alcohol has a primary alcohol group (—CH2OH) attached to a
16-to-36 carbon atoms long chain. Waxes are normally saturated and
are solids at room temperature.

Wax-ester of fatty acid and fatty alcohol

Plant waxes are usually found on leaves or seeds. Thus, cabbage leaf
wax consists of the primary alcohols C12 and C18—C28 esterified with
palmitic acid and other acids. The dominant components are stearyl and
ceryl alcohol (C26H53OH). In addition to primary alcohols, esters of sec-
ondary alcohols, for example, esters of nonacosane-15-ol, are present:

Waxes can be classified according to their origins as naturally occur-

ring or synthetic. The naturally occurring waxes can be classified into
animal, vegetable, and mineral waxes. Beeswax, spermaceti, wool
grease, and lanolin are important animal waxes. The vegetable waxes
include carnauba, ouricouri, and candelilla. Petroleum waxes are the
most prominent mineral waxes. Paraffin wax is petroleum wax con-
sisting mainly of normal alkanes with molecular weights usually less
than 450. Microcrystalline wax is another type of petroleum wax con-
taining substantial amounts of hydrocarbons other than normal alka-
nes, and the components have higher molecular weights than paraffin
wax components. Compositions of significant commercial waxes from
natural sources are given in Table 4.1 [I].

4.2 Fatty Acids

The carboxylic acids obtained from the hydrolysis of fat or oil are called
fatty acids. They are the building blocks of the triglycerides and the fats
and oils are often named as derivatives of these fatty acids. For exam-
ple, the tristearate of glycerol is named tristearin and the tripalmitate
of glycerol is named tripalmitin.
Normal saturated fatty acids have a long, unbranched hydrocarbon
chain having a general formula CH3(CH2)nCOOH, where n is usually
even and varies from 2 to 24.
The unsaturated fatty acids may have one double bond (monosatu-
rated) or have more than one ds-methylene interrupted double bond
(polyunsaturated) as illustrated in Fig. 4.1.
TABLE 4.1 Sources and Compositions of Normal Waxes

Melting
Type point 0C Main components
Animal waxes
Beeswax 64 Myricyl palmitate
Chinese Isoheptacosyl isoheptacosanoate,
82-84 ceryl lignocerate
Shellac Ceryl lignocerate, ceryl cerotate
Spermaceti 81-82 Cetyl palmitate
Wool (anhydrous Cholesteryl estolidic esters, alcohol
lanolin) 36-42 esters of iso- and anteiso acids
Mineral waxes
Montan 86 Tricontanyl esters of C28-3o acids
Petroleum waxes
Microcrystalline 71-88 Hydrocarbons (490-800 molecular weights)
Paraffin 54-57 Hydrocarbons (350-420 molecular weights)
Vegetable waxes
Bayberry 43-48 Trimyristin, tristearin
Candelilla 70-80 C29_33 hydrocarbons, simple esters and lactones
Carnauba 80-85 Esters of C26-3o alcohols and C26-3o co-hydroxy acids
Esparto 69-81 Hydrocarbons, esters of C26_32 acids and alcohols
Japan 51-62 Tripalmitin
Jojoba (a liquid wax) 11-12 Docosenyl eicosanoate
Ouricury 79-85 Myricyl cerotate and hydroxycerotate
Sugarcane 79-81 Myricyl palmitate stigmasteryl palmitate

SOURCE: Riegel's Handbook of Industrial Chemistry, 9th ed., 1992.

The following three systems of nomenclature are in use for naming

fatty acids.
a. The common (trivial) names
b. The number of carbon atoms in the chain
c. The International Union of Pure and Applied Chemistry (IUPAC)
system
The trivial names that indicate the initial source of fatty acids are used
more often than the IUPAC names in the industry. For example, butyric
acid is a major component of butter flavor, palmitic acid comes from palm
kernel, and oleic acid from olives.
The number of carbon atoms in the chain, followed by a colon and addi-
tional numbers indicating the number of double bonds, are used as an
abbreviation to designate fatty acids. Thus in the 18-carbon series,
C18:0, C18:l, C18:2, and C18:3 represent stearic, oleic, linoleic, and
linolenic acids, respectively. One or two letter abbreviations are also
used, and these four acids sometimes are designated by St, O, L, and
Ln, respectively.
 Stearic acid Saturated

Oleic acid Mono-unsaturated

Linolenic acid Polyunsaturated

Linolenic acid

y - Linolenic acid

Arachidonic acid-important fatty acid for animals

Figure 4.1 The structure of some fatty acids.

The IUPAC name of fatty acid is that of the alkane parent with the
-e changed to -oic acid. The carboxyl carbon is carbon 1:
CH3.CH2.CH2.CH2.CH2.CH2.CH2.CH3 (octane)
8 7 6 5 4 3 2 1
CH3.CH2.CH2.CH2.CH2.CH2.CH2.COOH (octanoic acid)
The suffix dioic is used if the acid contains two carboxyl groups.
The double bonds in fatty acids differ in (a) number, (b) location, (c)
geometrical configuration, and (d) conjugation. Conjugation is a special
case of location in which two double bonds are separated only by a single
carbon-carbon bond. Unsaturated fatty acids may have one or as many
as six double bonds. Those containing multiple double bonds usually
have a methylene (CH2) group between the double-bond sequence, so the
system is not conjugated.
 When double bonds are present, the suffix anoic is changed to enoic,
dienoic, or trienoic to indicate the number of bonds present. The location
of the first carbon in the double bond is indicated by a number preceding
the IUPAC systematic name. The geometric configuration of double bonds
is indicated by the Latin prefixes cis- (both hydrogens on one side) and
trans- (hydrogen across from each other). Unsaturation between the 9 and
10 carbons with cis orientation is most common in polyunsaturated fatty
acids. Accordingly, oleic, linoleic, and linolenic acids are called 9-octade-
cenoic, 9,12-octadecadienoic and 9,12,15-octadecatrienoic acids, respectively.
Table 4.2 lists some common examples of fatty acids, their sources,
common names, and systematic names [I]. Many additional terms are
used to distinguish unsaturated fatty acids by the location of the first
double bond relative to the omega (co) or —CH3 carbon. Thus oleic acid
is both A9 and a C18:l co-9 acid. Linoleic acid is a A9'12 and C18:2 co-6 acid.
Linolenic acid is both A9'12'15 and a C18:3 co-3 acid.

TABLE 4.2 Some Important Fatty Acids, Their Names and Common Sources

Carbon Common Systematic Common

atoms name name sources
Saturated fatty acids
3 Propionic Propanoic Bacterial fermentation
4 Butyric Butanoic Milk fats
5 Valeric Pentanoic Bacterial fermentation
5 Isovaleric 3-Methylbutanoic Dolphin and porpoise fats
6 Caproic Hexanoic Milk fats, some seed oils
8 Caprylic Octanoic Milk fats, Palmae seed oils
10 Capric Decanoic Sheep and goat milk, palm seed
oils, sperm head oil
12 Laurie Dodecanoic Coconut oil
14 Myristic Tetradecanoic Palm and coconut oils
16 Palmitic Hexadecanoic Palm oil
18 Stearic Octadecanoic Animal fats
19 Tuberculostearic 10-Methylstearic Tubercle bacillus lipids
20 Arachidic Eicosanoic Some animal fats
22 Behenic Docosanoic Peanut and various other
seed oils
24 Lignoceric Tetracosanoic Minor amounts in some
seed oils
26 Cerotic Hexacosanoic Plant waxes
28 Montanic Octacosanoic Beeswax and other waxes
30 Mellisic Triacontanoic Beeswax and other waxes
Unsaturated fatty acids
10 Caproleic 9-Decenoic Milk fats
10 Stillingic 2,4-Decadienoic Stillingia oil
12 Lauroleic 2-Dodecenoic Butterfat
18 Linolenic 9,12,15-Octadecatrienoic Linseed oil
SOURCE: Riegel's Handbook of Industrial Chemistry, 9th ed., 1992.
4.3 Glycerides
Glycerol can be esterified commercially with one, two, or three fatty
acids to produce mono-, di-, or triglycerides. Fats and oils are naturally
occurring triglycerides, the distribution of which varies in different
plants and animals.

Fatty acids

(Glycerol)
(A fat with three different
carboxylic acid-triglyceride)

The properties of triglycerides depend on the fatty acid composition and

on the relative location of fatty acids on the glycerol. As accurate meth-
ods for determining the composition are available, several conventions
have been developed to specify arrangements of fatty acids on the glyc-
erol molecule. Natural fats and oils are designated as the triglyceride type
in terms of saturated and unsaturated acids and isomeric forms.
Table 4.3 illustrates the triglyceride types and isomeric forms of some
natural fats. GS3 in the table refers to a fully saturated glyceride and
GS2U refers to a glyceride composed of two saturated acids and one
unsaturated acid. Distinguishing between the 1, 3, and 2 positions per-
mits identification of the SUS and SSU isomers of GS2U and the USU
and UUS isomers of GSU2.
A stereospecific numbering system (Sn) is used to indicate the loca-
tion of specific fatty acids in triglyceride molecules such as in 1-stearoyl-
2-oleoyl-3-myristoyl-Sn-glycerol; the respective fatty acids are indicated
in the 1, 2, and 3 positions. This kind of information is very valuable in
relating properties of certain fats to compositional data. Table 4.4

TABLE 4.3 Triglyceride Types and Isomeric Forms of Natural Fats

Types (% wt) Isomers (% wt)

GS3 GS2U GSU2 GU3 SUS SSU USU UUS
Pig fat (lard) 2.5 22.4 55.7 19.4 1.0 21.4 46.9 8.8
Peanut oil 0.1 9.9 42.5 47.5 9.3 0.6 0.7 41.8
Beef fat (tallow) 12.6 43.7 35.3 8.4 30.6 13.1 3.4 31.9
Cocoa butter 7.1 67.5 23.3 2.1 65.0 2.5 0.2 23.1
Soybean oil 0 3.7 31.0 65.3 3.7 0 0 31.0
TABLE 4.4 Fatty Acid Composition of Some Edible Oils and Fats
Source <14:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 20:1 22:0 22:1 24:0 24:1
Almond oil 0.0 6.5 0.6 1.7 69.4 17.4
Avocado oil 11.0 3.4 0.7 71.5 12.0 1.5
Butter fat 23.8 8.2 21.3 1.8 9.8 20.4 1.8 1.2
Canola oil 4.8 0.5 1.6 53.8 22.1 11.1 1.1 1.5 0.3 0.1 0.1
Cocoa butter 0.1 25.4 0.2 32.2 32.6 2.8 0.1 0.0
Coconut oil 58.7 16.8 8.2 2.8 5.8 1.8
Corn oil 0.0 0.0 10.9 1.8 24.2 58.0 0.7
Cotton seed oil 0.8 22.7 0.8 2.3 17.0 51.5 0.2
Fish (manhaden) oil 9.6 20.5 12.6 3.3 11.0 0.7 1.6 0.3 0.8
Lard 0.5 1.3 23.8 2.7 13.5 41.2 10.2 1.0 1.0
Mustard seed oil 0.1 1.9 0.3 0.1 17.7 9.1 0.5 0.6 3.91 1.8 55.1 0.2 1.9
Olive oil 0.0 11.0 0.8 2.2 72.5 7.9 0.6
Palm oil 0.1 1.0 43.5 0.3 4.3 36.6 9.1 0.2 0.1
Palm kernel oil 54.2 16.4 8.1 2.8 11.4 1.6
Peanut oil 0.1 9.5 0.1 2.2 44.8 32.0 1.3 1.8
Rapeseed oil 1.7 0.9 12.3 12.7 7.6 1.2 0.9 59.4 0.5 1.6
Rice bran oil 0.7 16.9 0.2 1.6 39.1 33.4 1.6
Safflower oil 0.1 6.2 0.4 2.2 11.7 74.1 0.4 5.8
Sesame oil 8.9 0.2 4.8 39.3 41.3 0.3
Soybean oil 0.1 10.3 0.2 3.8 22.3 51.0 6.8
Sunflower oil 5.4 0.2 3.5 80.6 8.4 0.2 0.3 0.2
Tallow 0.9 3.7 24.9 4.2 18.9 36.0 3.1 0.6
Walnut oil 7.0 0.1 2.0 22.2 0.4 52.9 10.4
0.3
SOURCE: Riegel's Handbook of Industrial Chemistry, 9th ed., 1992.
summarizes general distribution for the major edible fats and oils,
and Table 4.5 that for industrial fats and oils [I].

4.4 Physical Properties of Triglycerides

The physical properties, such as melting points, specific heat, viscosity,
density, and refractive index depend on the type of fatty acids present
in the triglyceride and their location, chain length of fatty acids, number
and location of cis and trans double bonds on the fatty acid chains as
well as compatibility of the different triglycerides in the mixture and the
type of crystal present.

4.4.1 Melting point

The melting point of fats usually occurs over a wide range of tempera-
ture. The melting range of fats depends on the triglyceride composition.
Among the fatty acids, melting points increase with chain length. Trans
fatty acids always have higher melting points than their cis counterparts
for any chain length. Melting point data are useful in animal fats and
processed fats but are of little value for vegetable oils because most oils
are liquids at ambient temperatures.

4.4.2 Specific heat

The specific heat of fats is defined as the ratio of the heat capacity of a
fat to the heat capacity of water; or the quantity of heat required for a
one-degree temperature change in a unit weight of fats. Although the
specific heat of most triglycerides in a given physical state are similar,
specific heat does increase with increasing unsaturation of fatty acids
in both the liquid and solid states of a fat. Liquid fats have almost twice
the specific heat values than those of solid fats. Knowledge of the spe-
cific heat of fats and oils is useful in processing operation.

4.4.3 Viscosity
Viscosity of an oil or a fat is a measure of its resistance to flow. Viscosity
is an important factor in designing systems for handling oils and fats.
Among the fatty acids, viscosity increases with chain length and
decreases with increasing unsaturation. Viscosity is thus a function of
molecular size and orientation of the molecules. There is an approxi-
mately linear relationship between log viscosity and temperature. The
viscosity of oils usually increases in prolonged heating as a result of poly-
merization (gum formation).
TABLE 4.5 Fatty Acid Composition of Some Industrial Oils and Fats
Source <14:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 20:1 22:0 22:1 24:0 24:1
Castor oil 1.1 0.2 3.3 3.6 0.32 0.4
Chinese tallow 1.3 2.1 65 4.4 22.5 0.8
Croton oil 2.5 5.4 6.2 0.2 3.2 15.8 49.4 3 2.9 8.9 0.2 0.6
Jojoba oil 9 70.7 16.3
Linseed oil 5.3 4.1 20.2 12.7 53.3
Rapeseed oil 0.1 2.6 0.3 0.9 11.2 12.8 8.6
Tall oil 50 7 41 7.5 48.1
Tung oil 3.1 2.1 11.2 14.6 69
Whale oil 3.3 8.1 26.9 1.1 33.3
10.9 2.2
SOURCE: Riegel's Handbook of Industrial Chemistry, 9th ed., 1992.
4.4.4 Density
The density of fats and oils is an index of the weight of a measured
volume of the material. This property is important not only for design-
ing of equipment but also for the estimation of the solid fat index (SFI).
The SFI is related, approximately, to the percentage of solids in a fat at
a given temperature. When determined at a number of specified tem-
peratures, it can be especially useful to margarine manufacturers or
other processors who need to control the characteristics of their manu-
factured products by blending.

4.4.5 Refractive index

The refractive index of fats and oils is sensitive to composition. The
refractive index of a fat increases with increasing chain length of fatty
acids in the triglycerides or with increasing unsaturation. This makes
it an excellent spot test for uniformity of compositions of oils and fats.
Further, the refractive index is an additive as well as constructive prop-
erty, thus it can be used as a control procedure during hydrogenation
processes.

4.4.6 Polymorphism
The existence of a substance in two or more forms, which are signifi-
cantly different in physical or chemical properties, is known as poly-
morphism. The difference between the forms arises from different modes
of molecular packing in the crystal structure of certain triglycerides.
Certain pure or mixed fatty acid triglycerides may show as many as five
different melting points. Each crystal system has a characteristic melt-
ing point, x-ray diffraction pattern, and infrared spectrum. For example,
tristearin can exist in three polymorphic forms with melting points of
54.7, 63.2, and 73.5°C.
An awareness of crystal-packing characteristics and polymorphism
helps one to understand incompatibility problems of different fats.
Polymorphism has several industrial implications in use of fats as short-
enings, margarines, and cocoa butter.

4.4.7 Other physical properties

Other physical properties such as the smoke, flash, and fire points of oils
and fats are measures of their thermal stability when heated. The smoke
point is important for the oils and fats used for deep-frying. The flash
point and fire points are a measure of residual solvent in crude and
refined oils and are also a safety requirement.
Table 4.6 shows some physical properties of oils and fats [I].
TABLE 4.6 Physical Properties of Oils and Fats
Rapeseed Peanut Cottonseed Soybean Sunflower Coconut Palm Olive Beef
Properties oil oil oil oil oil oil oil oil tallow Lard
3
1) Density @15°C g/cm 0.910 0.991 0.917 0.922 9.20 0.919 0.921 0.914 0.936 0.914
2) R.I. @20°C 1.472 1.460 1.472 1.470 1.474 1.448 1.453 1.467 1.454 1.458
3) Smoke Pt.°C 218 207 223 213 209 200 223
4) Flash Pt.°C 317 315 322 317 316 300 314 316
5) FirePt.°C 344 342 342 342 341 341 344
6) Viscosity @50°C n.m.pa.s 30 23 27 25 26 19 28 30 25 25
7) Sp. Heat J/g 2.18 2.06 2.50 2.40
@79.6°C @80.4°C @175°C @140°C
4.5 Chemical Properties of Triglycerides
The most important chemical reactions for triglycerides (fats and edible
oils) are hydrolysis, methanolysis, and interesterification. The other
reactions, such as hydrogenation, isomerization, polymerization, and
autoxidation that are primarily relevant to the processing of edible oils
and fats are also discussed in this section.

4.5.1 Hydrolysis
The fat or oil can be hydrolyzed into fatty acids and glycerol by treat-
ment with steam under elevated pressure and temperature. The reac-
tion is reversible and is catalyzed by inorganic catalysts (ZnO, MgO, or
CaO) and an acid catalyst (aromatic sulfonic acid).
CH2OCOR CH2OH
CHOCOR + 3H2O ^ CHOH + 3RC00H
I I
CH2OCOR CH2OH

Glycerides can also be hydrolyzed by treatment with alkali (saponi-

fication). After acidification and extraction, the free fatty acids are recov-
ered as alkali salts (soaps).
CH2OCOR CH2OH
CHOCOR + 3KOH ^ CHOH + 3RC00K
I I
CH2OCOR CH2OH

4.5.2 Methanolysis
The fats and oil react with methanol to produce fatty methyl esters.
Inorganic alkali, quaternary ammonium salts, and enzymes (lipase)
have been used as catalysts for methanolysis in commercially practiced
processes for soap manufacture.
CH2OCOR CH2OH
CHOCOR + 3CH3OH • } RCOOCH3 + CHOH
(W>COR +Na0H CH2OH

3RCOONa + CH3OH

4.5.3 Interesterification
Interesterification causes a fatty acid redistribution within and among
triglyceride molecules, which can lead to substantial changes in the
physical properties of fats and oils or their mixtures without altering the
chemical structure of the fatty acids. Intermolecular acyl groups
exchange triglycerides in the reaction until an equilibrium is reached,
which depends on the structure and composition of the triglyceride mol-
ecules. The reaction is very slow even at 200 to 3000C, but the rate of
reaction can be accelerated by using sodium methylate.

Interesterification may be either random or directed. In random inter-

esterification the acyl groups are randomly distributed as demonstrated
by the following example where equal proportions of tristearin (S—S—S)
and triolein (O—O—O) are allowed to interesterify.

In directed interesterification, the reaction temperature is lowered

until the higher-melting and least-soluble triglyceride molecule in the
mixture crystallizes. In this way, a fat can be separated into higher and
lower melting fractions.

The directed interesterification is of much industrial significance

because it can be used to convert oils into more and/or less saturated
fractions of original fat or oil or blend of two oils.

4.5.4 Hydrogenation
The unsaturated double bonds in a fatty-acid chain are converted to sat-
urated bonds by addition of hydrogen. The reaction between the liquid
oil and hydrogen gas is accelerated by using a suitable solid catalyst such
as nickel, platinum, copper, or palladium. Hydrogenation is exothermic,
and leads to an increase in melting point and drop in iodine value.
Partial hydrogenation can lead to isomerization of cis double bonds
(geometrical isomerization).
Polyunsaturated fatty acids such as linolenic acid (C18:3) are hydro-
genated more quickly to linoleic (C18:2) or oleic acid (C18:1) than linoleic
to oleic acid or oleic acid to stearic acid (C18:0). The conversion steps can
be represented as follows:

4.5.5 Isomerization
The configuration of the double bond in naturally occurring fatty acids,
present in oils and fats, is predominantly in the cis form. Isomerization
can occur if oils and fats are heated at temperatures above 1000C in the
presence of bleaching earths or catalysts such as nickel, selenium, sulfur,
or iodine.
Two types of isomerization spontaneously occur during hydrogenation:
geometrical and positional. The extent to which isomerization occurs can
be affected by processing conditions and catalyst selection.

4.5.6 Polymerization
Under deep-frying conditions (200 to 3000C) the unsaturated fatty acids
undergo polymerization reactions forming dimeric, oligomeric, and poly-
meric compounds. The rate of polymerization increases with increasing
degree of unsaturation: saturated fatty acids are not polymerized. In
thermal polymerization polyunsaturated fatty acids are first isomerized
into conjugated fatty acids, which in turn interact by Diels-Alder reac-
tions producing cyclohexene derivatives. The cyclohexene ring is read-
ily dehydrogenated to an aromatic ring; hence compounds related to
benzoic acid can be formed.
On the other hand, oxidative polymerization involves formation of
C —O —C bonds. Polymers with ether and peroxide linkages are formed
in the presence of oxygen. They may also contain hydroxy, oxo, or epoxy
groups. Such compounds are undesirable in deep-fried oil or fat because
they permanently diminish the flavoring characteristics of the oil or fat
and also cause a foaming problem.

4.5.7 Autoxidation
Fats and oils often contain double bonds. Autoxidation of a fat or oil
yields a mixture of products that include low molecular weight car-
boxylic acids, aldehydes, and methyl ketones.
 Drying oils such as linseed oil contain many double bonds. These oils
are purposely allowed to undergo air oxidation leading to a tough poly-
mer film on the painted surface.
The autoxidation reactions involve three steps: initiation, propagation,
and termination. The initiation step leads to the formation of a hydroper-
oxide on a methylene group adjacent to a double bond; this step proceeds
via a free-radical mechanism:

(H abstraction)

Hydroperoxide

The second step, which is also a reaction in the propagation cycle, is the
addition of another molecule to the hydroperoxide radical to generate
new free radicals.
The chain length of these two radical-reaction steps is about 100.
When the radical concentration has reached a certain limit, the chain
reaction is gradually stopped by mutual combination of radicals, the
termination step.
Numerous compounds result from these reactions. For example,
Table 4.7 lists a series of aldehydes and methyl ketones derived pref-
erentially when tristearin is heated in air at 192°C [2].

TABLE 4.7 Oxidation Products of Tristearin

Class of Major
compounds % Portion C-number compounds

Alcohols 2.7 4—14 n-Octanol, n-Nonanol, n-Deanol

v-Lactones 4.1 4-14 v-Butyroactone, v-Pentalactone,
v-Heptalactone
Alkanes 8.8 4-17 n-C 7 , nC- 9 , nC- 10
Acids 9.7 2-12 Caproic, Butyric
Aldehydes 36.1 3-17 n Hexanal, n Octanal
Methyl ketones 38.4 3-17 2-Heptanone, 2-Decanone
4.6 Sources of Edible Oils and Main Fats
Several hundred plants and animals produce fats and oils in sufficient
quantities to warrant processing into edible oils; however, only a few
sources are commercially significant. Table 4.8 summarizes the major
sources in the world and the method of processing.
The organ fats of domestic animals, such as cattle and hogs, and milk
fat are important raw materials for fat production. Edible oils are mostly
of plant origin. Olive oil and palm oil are extracted from fruits. All other
oils are extracted from oilseeds. The world production of oilseeds and
other crops has significantly increased in recent years to meet the grow-
ing needs for oils and fats in the world.
World oilseed production in 2003 was 335.9 million tons [3]. Figure 4.2
shows world production of the different oilseeds. Soybeans constitute the
largest share (56 percent) and the United States is the main crop-grower.
Malaysia grows mainly palm. The Philippines grows coconut. China,
Europe, India, and Canada grow rapeseed (canola). Sunflower is grown
in the United States, Australia, Europe, and Argentina. The cottonseed
market is dominated by the United States, China, Pakistan, India, and
the former Soviet Union.
World vegetable oil consumption in 2003 was 87.2 million tons. U.S.
consumption was 9.91 million tons. In the U.S. market, animal fats (tallow
and lard) have a relatively small share (2 percent) compared to vegetable
oils. The consumption of four oils—soybean (80 percent), corn (4 percent),
canola (4 percent), and cottonseed (3 percent) has grown rapidly over the
past 30 years compared to the traditional oils and animal fats. Figure 4.3
shows U.S. consumption of edible fats and oils in 2003 [3].

TABLE 4.8 Major Edible Fats and Oils in the World and Methods of Processing

Prevalent method
Source Oil content (%) of recovery
Soybean 19 Direct solvent extraction
Corn (germ) 40 Wet or dry milling and prepress
solvent extraction
Tallow (edible tissue) 70-95 Wet or dry rendering
Canola 42 Prepress solvent extraction
Coconut (dried copra) 66 Hard pressing
Cottonseed 19 Hard pressing or prepressing or
direct solvent extraction
Lard (edible tissue) 70-95 Wet or dry rendering
Palm 47 Hard pressing
Palm kernel 48 Hard pressing
Sunflower 40 Prepress solvent extraction
Peanut (shelled) 47 Hard pressing or prepress
solvent extraction
 Soybeans
56%
Copra
2%

Palm kernel
2%

Rapeseed
Sunflowerseed 12%
8% Peanut Cottonseed
10% 10%

Million short tons Million metric tons

Soybeans 209.5 190.1
39
Rapeseed 43
3 2
Cottonseed 38.7 ^
Peanut 35.4 26
Sunflowerseed 28.7 8.1
Palm kernel 8.9 5.4
335 9
Copra 5.9 -
Total 370.1
Source: USDA
Figure 4.2 World oilseed production 2003.

4.7 Oils and Fats: Processing and Refining

Crude fats and oils consist primarily of glycerides. However, they also
contain many other lipids in minor quantitites. Corn oil, for example, may
contain glycerides plus phospholipids, glycolipids, many isomers of sitos-
terol and stigmasterol (plant steroids), several tocopherols (vitamins E),
vitamin A, waxes, unsaturated hydrocarbons such as squalane and
dozens of carotenoids and chlorophyll compounds, as well as many prod-
ucts of decomposition, hydrolysis, oxidation, and polymerization of any
of the natural constituents.
All crude oils and fats obtained after rendering, crushing, or solvent
extraction, inevitably contain variable amounts of nonglyceridic cocon-
stituents like fatty acids, partial glycerides (mono- and diglycerides),
phosphatides, sterols, tocopherols, hydrocarbons, pigments (gossypol,
chlorophyll), vitamins (carotene), sterol glucosides, protein fragments
as well as resinous and mucilaginous materials, traces of pesticides, and
 Soybeans
80%

(Other 1)
10%

Peanut
1% Canola (rapeseed)
Coconut Lard 4%
1% 1% Cottonseed
Edible tallow 2%
1%
Million pounds Million metric tons
Soybeans 17,471 7.92
Canola (rapeseed) 857 0.39
Cottonseed 482 0.22
Lard 205 0.09
Edible tallow 236 0.11
Coconut 310 0.14
Peanut 185 0.08
(Other 1) 2,112 0.96
Total 21,858 9.91
Source: USDA
Figure 4.3 U.S. fats and oils edible consumption, 2003.

"heavy" metals. Table 4.9 shows some of the most important cocon-
stituents found in some major oils [4].
Some of these materials are highly undesirable and must be removed
to provide satisfactory processing characteristics and to provide desir-
able color, odor, flavor, and keeping qualities in the finished products.

TABLE 4.9 Minor Components in Some Major Oils

Component Soybean oil Canola Palm oil

FFA 0.3-0.8% 0.3-1.0% 2.0-5.0%
Phosphatides 1.0-3.0% 0.5-3.5% 0.03-0.1%
Sterols/triterpenic alcohols 0.04-0.07% 0.04-0.6% 0.1-0.2%
Tocopherols/tocotrienols 0.06-0.2% 0.06-0.1% 0.05-0.1%
Carotenoids 40-50 ppm 25-70 ppm 500-800 ppm
Chlorophyll/pheophytine 1-2 ppm 5-30 ppm Traces
Peroxides meg O2/kg <10 <10 1-5
Fe 1-3 ppm 1-5 ppm 4-10 ppm
Cu 0-30 ppb 0-30 ppb 0-50 ppb
These objectionable coconstituents are removed during the refining
process in such a way that the glyceride yield and the desirable con-
stituents in the oil are not affected.
Figure 4.4 shows the different stages in seed preparation and a classi-
cal chemical refining process. The general methods employed to produce
edible oils suitable for human consumption consist of (a) seed prepa-
ration, (b) extraction, (c) degumming, (d) neutralization, (e) bleaching,
(f) deodorization, (g) hydrogenation, and sometimes winterization.

Cleaned dried
oil seed

Hulls or Dehulling or
shells deshelling

Crush tc
pulp

Screw
Oil (virgin)
press

Water Pulp dried

refining to flakes

Solvent Solvent
extractor (hexane)

Solvent Solid
removal product

Alkali Drying
refining

Meal
Bleaching

Filter

Deodorizing

Waterization/
Refined hydrogenation
oil (if required)

Figure 4.4 Essential steps in the extracting and refining of

edible oil from oilseeds.
Seed preparation. When oilseeds are received at the oil mill, they still
contain plant residues, damaged seeds, dust, sand, wood, pieces of metal,
and foreign seeds. The oilseeds are carefully cleaned of these materials
using magnets, screens, and aspirator systems. The cleaned seeds are
dried to remove moisture. Next, the dried oilseeds are usually decorti-
cated to remove the hull that surrounds the oilseed meat before being
further processed. Hulls always contain much less oil than kernels or
meats. Further, removing the hull reduces the amount of material that
must be handled, extracted, and refined. Dehulling is normally pre-
formed very carefully, to ensure that the meat is not broken into too
many small pieces. Corrugated roller mills or bar mills are used to cut
or break the hull to free the meat. The hulls are separated by screen-
ing and air clarification. Hulls may be blended back with meat to con-
trol protein level, sold as a cattle feed, or burned in boilers to generate
steam and electrical energy.

Extraction. The raw material for the fat and oil industry comes from ani-
mals (hogs, sheep, and fatty fish); fleshy fruits (palm and olive); and var-
ious oilseeds. Most oilseeds are grown specifically for processing of oils
and protein meals.
The purpose of oil extraction is twofold: first, extracting the maximum
amount of good quality oils and then getting maximum value from the
residual press cake or meal. The following three methods, with varying
degrees of mechanical simplicity, are used: (1) rendering, (2) pressing
with mechanical presses, and (3) extracting with a volatile solvent.

Rendering. The rendering process is applied on a large scale to the pro-

duction of animal fats, such as tallow, lard, bone fat, and whale oil. The
fatty tissues are chopped into small pieces and are boiled in steam
digesters. The fat is gradually liberated from the cells and floats to the
surface of the water, where it is collected by skimming. A similar method
is used in the extraction of palm oil from fresh palm fruits.

Pressing. Oil seeds do not have fat cells like those of animals for stor-
ing fats. Instead oil is stored in microscopic globules throughout the cells.
In these cases, rendering will not liberate the oil from the cellular struc-
tures and the cell walls are broken only by grinding, flaking, rolling, or
pressing under high pressures to liberate the oil. The general sequence
of modern operations in pressing oilseeds and nuts is as follows:
(1) Preparation of the seed to remove stray bits of metals and removal
of hulls; (2) Reduction of particle size of the kernels (meats) by grind-
ing; and (3) Cooking and pressing in hydraulic or screw presses.
Efficient oil extraction by a mechanical press is highly dependent on
having the correct preparation before pressing. The extraction stage
 Feed

Cage

Screw
Press
cake

Oil
Figure 4.5 Screw press.

itself is carried out using a screw press (Fig. 4.5). The press is fed by
means of a variable speed conveyor, within the feeder unit. The feeder
regulates the flow of material into the press and thereby controls the
loading on the press main motor. Oil released along the length of the cage
is allowed to drain into the base of the press where it is collected. The
solid material (press cake) remaining within the press is finally discharged
into conveyors to be removed for subsequent processing or storage [5],
Oil expressed without heating contains the least amount of impuri-
ties and is often of edible quality without refining or further processing.
Such oils are known as cold-drawn, cold-pressed, or virgin oils. The
expressed oil from cooked seeds contains greater quantities of nonglyceride
impurities such as phospholipids, color bodies, and unsaponifiable matter.
Such oils are highly colored and are not suitable for edible use.

Solvent extraction. The press cake emerging from a screw press still
retains 3 to 15 percent of residual oil. More complete extraction is done
by solvent extraction of the residues obtained from mechanical press-
ing. The greater efficiency obtained in the solvent extraction process
encouraged the industry for direct application to oilseeds. In the United
States and Europe, continuous extractor units are used in which fresh
seed flakes are added continuously and are subjected to a counterflow
of solvent by which intimate contact is achieved between the seeds and
solvent. The common solvent for edible oil is commercial hexane or
heptane, commonly known as petroleum ethers, boiling in the range of
146 to 156°F (63.3 to 68.9°C). After extraction, maximum solvent recov-
ery is necessary for economical operation. The solvent is recovered by dis-
tillation and is reused. The extraction oil is mixed with prepress oil for
refining. The extracted meals contain less than 1 percent of residual oil.
In large-scale operations, solvent extraction is a more economical
means of recovering oil than mechanical pressing.
Refining (degumming and neutralization). The usual refining of vegetable
oils involves degumming and alkali refining. Degumming mainly
reduces the phosphatides and metal content of the crude oil by mixing
it with an acid and water. The phosphatides are present in free hydrat-
able form (HP) or in nonhydratable form (NHP), mostly in combination
with some Ca+*, Mg+*, or Fe+*. In alkali refining, the NHP that remains
behind in the oil after acid treatment, and the free fatty acids formed
during the hydrolysis (lipolysis) of the HP, are further removed by neu-
tralization.
Degumming consists of treating the oil with a small amount (0.05 per-
cent) of concentrated phosphoric acid and water, followed by centrifu-
gal separation of coagulated material (lecithin). The process is applied
to many oils (e.g., soybeen oil) that contain phospholipids in significant
amounts. Refining with alkali removes free fatty acids that are formed
during the lipolysis of the fat or oil before rendering or extraction. The
oil is treated with an excess of 0.1 percent caustic soda solution and
the mixture is heated to about 75°C to break any emulsions formed. The
mixture is allowed to settle. The settlings, called "foots," are collected
and sold as "soapstock." In the continuous system, the emulsion is sep-
arated with centrifuges. After the oil has been refined, it is usually
washed with water to remove traces of alkali and soapstock. After water
washing, the oil may be dried by heating in a vacuum or by filtering
through a dry filter and material.
A whole variety of processes have been developed to improve the
removal of the nonhydratable phosphatides. The best known are the uni-
and superdegumming processes (unilever) and the TOP degumming
process (vandemoortele). They are principally based on a special acid
treatment of the NHP. Over the last few years, several new technolog-
ical approaches have been developed, which guarantee very low levels
of phosphorus (less than 10 ppm).
In the enzymatic degumming process, part of the hydratable phos-
phatides is enzymatically modified by removing the fatty acid on the
C-2 position of the glycerol, using a phospholipase A2 enzyme as bio-
catalyst. These modified phosphatides facilitate the removal of the
remaining NHP. Table 4.10 shows the results of an enzymatic degumming

TABLE 4.10 Example of Enzymatic Degumming

Rapeseed oil Crude oil Degummed oil

Phospholipids 0.60% 0.01-0.02%

P 240 ppm 4-8 ppm
H2O 0.10% 0.30%

NOTE: P-content = phosphatide content x 104t/25.

of crude rapeseed oil. The phosphorus levels are reduced from 240 ppm
to 4-8 ppm [4].

Phospholipase A2

Buffer Ca/NaOH
(pH = 5)
Reaction time min. 3 hrs

Phosphatide Lyso-lecithin

In the soft-degumming process, a chelating agent (EDTA) is added to

the oil to remove the cations from the nonhydratable phosphatides,
thereby making them hydratable again (Table 4.11) [4].
"catalyst"
(phosphatide) phosphatide

In the improved acid degumming (IMPAC De Smet), special additives

are mixed to improve the wetting of the NHP and hence their solubility
in the aqueous phase [4]. Furthermore, an intimate contact between the
reaction products (acid/alkaline) and the phosphatides is ensured to
improve hydratability of the NHP and hence the efficiency of their
removal. However, in all dugumming processes the efficiency of the
degumming treatment depends to a great extent on the quality of the
crude oil. A good-quality fresh oil is easier to degum than an adulterated
oil. This is a direct consequence of the NHP to HP ratio: the lower the
NHP content, the easier the degumming procedure and the better the
degummed oil yield. Figure 4.6 summarizes the different steps of degum-
ming processes in the form of a process diagram [4].

TABLE 4.11 Example of Soft Degumming

Soybean oil Crude oil Degummed oil

Phospholipids 0.30% 0.01%
P* 120 ppm 3-5 ppm
Ca 59 0.1
Mg 35 0.02
Fe 1.6 0.04
NOTE: P-content = phosphatide content x 104/25.
Represents laboratory data.
 Crude oil Lecithins
Water
Mixing Drying

Separatic Hydratable phospholipids (HP)

Water degummed oil

Acid (citric/phosphoric acid): NHP HP
Mixing

Soaps
Mixing

Separation Non-hydratable phospholipids (NHP)

Acid degummed oil

Bleaching Deodorization

Figure 4.6 Generalized flow sheet for degumming process. (Source:

Courtesy of DeSmet Group, Antwerp, Belgium.)

Bleaching. The refined oils are usually dark in color owing to the pres-
ence of some pigmented materials such as chlorophyll or carotenoids and
minor impurities like residual phosphatides, soaps, metals, and oxi-
datin products. Bleaching reduces the color by absorbing these colorants
on bleaching earth (bentonite clays), or activated charcoal, or both. In
addition to decolorization, bleaching clay also absorbs suspended matter
and other minor impurities.
The bleaching process comprises three stages:
• Initial mixing of oil with bleaching earth.
• Oil heating under a vacuum with sparge steam to ensure complete
contact between the oil and the earth.
• Filtration on hermetic leaf filters, followed by polishing filtration. The
spent cake is dried by steam blowing and the recovered oil is recycled.
Natural bleaching clays are aluminum silicates (bentonite, atta-
pulgite, and montmorillonite), containing relatively high amounts of
Mg, Ca, or Fe. The clays are generally activated by heat treatment. The
high metal content, however, limits the adsorptive activity of these
clays. The metals can be removed from the reactive spots by means of
acid treatment, yielding clays with much higher adsorptive capacity. In
some cases, active carbon is added in the course of bleaching to improve
the removal of blue and green pigments as well as polycyclic aromatic
hydrocarbons. As a result of high cost and high-oil retention, active
carbon is used only in specific cases (e.g., coconut and palm kernel oil),
in combination with bleaching clays, mostly in a ratio of 1/10 to 1/20.
Bleaching is by far the most expensive process in refining in terms of
utilities cost. The relatively high cost of the bleaching clays as well as
the oil-in-earth losses and bleaching adsorbent disposal costs largely
affect the operating cost of a bleaching plant. Moreover, the ever stronger
environmental regulations are now forcing oil refiners to drastically
reduce mainly the solid wastes as these are the most difficult to treat.
Several bleaching processes have been developed over the years to
limit the consumption of bleaching earth. Figure 4.7 shows the flow
sheet of a double-batch bleaching process. This is by far the oldest
bleaching method, still in use in many refining plants [4].
In order to reduce bleaching earth consumption, alternative new mul-
tistep bleaching processes have been developed. Figure 4.8 shows the
flow sheet of a two-stage counter-current bleaching with a prefiltration
process. The main function of prefiltration is to remove all solid impu-
rities as well as to adsorb most of the phosphatides and soaps. This
increases bleaching efficiency in the second stage [4].

Bleaching earth
Vacuum unit

Double batch bleacher Filter

Polishing filter

Bleached oil

Acid pretreatment

Citric acid

Crude oil

Figure 4.7 Flow sheet of a double batch bleaching process with acid pretreatment.
(Source: Courtesy of DeSmet Group, Antwerp, Belgium.)
Vacuum unit

Bleached c

Prefiltration Vacuum

Oil
inlet
Safety filte
Final
Bleaching filtration
earht dosing

Final
bleaching

Figure 4.8 Two-stage counter-current bleaching with prefiltration. (Source: Courtesy of

DeSmet Group, Antwerp, Belgium.)

Deodorization. Most fats and oils, even after refining, have characteris-
tic flavors and odors owing to the presence of minor amounts of free fatty
acids, aldehydes, ketones, and other compounds. The concentration of
these undesirable substances, found in most oils, is generally low, between
0.2 and 0.5 percent. The efficient removal of undesirable substances
depends on (a) the vapor pressure of the different minor compounds,
(b) the deodorizing conditions (temperature, pressure, residence time),
(c) the amount of stripping steam, and (d) the geometry of the vessel (e.g.,
sparge-steam distribution, oil depth, stainless steel, and so on.).
Deodorization is usually conducted at a temperature between 220
and 2600C, at a pressure between 2 and 4 mbar, and under injection of
0.5 to 3 percent steam in a stainless steel vessel.
The different stages in the deodorization process are as follows:

• Deaeration
• Heating
• Deodorization or steam stripping
• Heat recovery or cooling
• Final cooling

The volatiles, evaporated during deodorization, are condensed and are

usually recovered in a direct condenser or scrubber for fatty substances.
Both batch and continuous deodorization processes are used. The batch
deodorizer is the earliest and most simple type of process. It generally
 Vacuum unit

Deodorizer Fatty
acids
scrubber
Heating
steam

Cooling
Sparge Fatty
Cooling
steam acids
water To clean
water
Oil to
deodorized
Cooling
Deodorized
Polishing
filter

Figure 4.9 Batch deodorization process. (Source: Courtesy of DeSmet Group, Antwerp,
Belgium.)

uses a single-shell vertical cylindrical vessel to perform all desired func-

tions (Fig. 4.9). These units are used for small capacities (less than
50 TPD) and irregular production or to process small batches of multiple
oils that demand minimum intermixing [4].
The continuous deodorizer performs the same basic functions but is
designed for a larger operation, requiring few feedstock changes (Fig. 4.10).
It is generally the best choice for modern integrated refineries [4].
About 0.01 percent of citric acid is commonly added to deodorized oils
to inactivate trace-metal contaminants such as soluble iron or copper
compounds that would otherwise promote oxidation and the develop-
ment of rancidity.

Hydrogenation. Hydrogenation is used to convert liquid fats to plastic

fats, thereby making them suitable for the manufacture of margarine
or shortening. Hydrogenated oils and fats also exhibit improved oxida-
tive stability and color. Close control of hydrogenation results in highly
specific results. For example, salad and cooking oils can be improved by
controlled hydrogenation.
In the hydrogenation process, the hydrogen is added directly to double
bonds of fatty acids. The most unsaturated fatty acid groups are most
easily hydrogenated and thus react first with the hydrogen if conditions are
 Vacuum unit

Deodorizer
Heating
tray Fatty
High pressure acids
steam boiler scrubber

Deodorizing
tray
Fatty
acids
Bleached Cooling
tray
Polishing Oil cooling
filter

Deodorized
oil
Polishing
Deodorizer filter
Dearation

Figure 4.10 Continuous deodorization process. (Source: Courtesy of DeSmet Group,

Antwerp, Belgium.)

somewhat selective, that is, to add hydrogen to the linolenic (three double
bonds) and linoleic (two double bonds) acid radicals before adding to the oleic
(one double bond) acid radicals. The reaction may be generalized:

Raney nickel-type and copper-containing catalysts are normally used.

Variables affecting hydrogenation include the catalyst, temperature,
hydrogen pressure, and amount of agitation. If very hard fats with low
amounts of unsaturation are derived and selectivity is unimportant,
higher temperatures and pressures are employed to shorten the reaction
time and to use the partially spent catalyst that would otherwise be
wasted. The catalytic hydrogenation is frequently accompanied by
isomerization with a significant increase of melting point, caused, for
example, by oleic (cis) isomerizing to olaidic (trans) acid. The trans isomers
are much higher melting than natural cis forms. After hydrogenation,
hot oil is filtered to remove the metallic catalyst for either reuse or recovery.

Winterization. Winterization is an operation that consists in removing

from certain oils the components that solidify at low temperatures and
therefore are a source of turbidity or settling in the bottle. The process
consists in filtering cooled oil under strict control.
Winterizing is not practiced so widely in hot countries and its appli-
cation is restricted mainly to sunflower, maize, cotton, olive, ricebran, and
partially hydrogenated soybean oils. The feedstock of the winterizing
plant is usually bleached oil, sometimes neutralized or deodorized oil.
The winterizing process is conducted in four steps:
• the oil is precooled in heat exchangers;
• the filter aid is added just before the first crystallizer and the oil is
cooled slowly, in a minimum of 6 h, a prerequisite for gentle crystal-
lization;
• the crystallized form stays 6 h in the maturator, at final cooling
temperature;
• the oil is then filtered in horizontal hermetic leaf filters. The oil tem-
perature is often raised just before filtration, to reduce viscosity and
hence facilitate filtration.
Normally, a winterized oil should remain clear for at least 24 h at 00C.
This corresponds to a wax content of below 50 ppm.

4.8 Fats and Oils Stability and Antioxidants

The capability of a fat, oil, or fatty food to retain a fresh taste and odor
during storage and use is referred to as its stability. It is related to the
ester linkages of triglycerides, which are either subjected to hydrolysis
liberating free fatty acids (lipolysis), or may undergo oxidation forming
peroxides and aldehydes (oxidation). Lipolysis can occur from chemical,
enzymatic, or thermal stress actions. Lipolytic spoilage is known as
lipolytic rancidity, or hydrolytic rancidity. Fats and oils also can become
rancid as a result of oxidation and this oxidative spoilage is known as
oxidative rancidity. Lipolytic rancidity usually poses less of a flavor
problem than oxidative rancidity because the former develops off-flavor
only in those fats, which contain short-chain fatty acids (less than C12).
Oxidation of fats and oils is thought to be the major cause because of
which the ester linkages of triglycerides in polyunsaturated oil deteri-
orate. The reaction of oxygen with unsaturated fatty acids in fats and
oils proceeds through a free-radical chain-reaction mechanism involv-
ing three stages: (1) initiation-formation of free radicals; (2) propagation-
free-radical chain reaction; (3) termination-formation of nonradical
products. Hydroperoxides are the major initial-reaction products of fatty
acids with oxygen. Subsequent reactions control both the rate of reac-
tion and the nature of products formed. The initiation step is the removal
of weakly held methylene hydrogen to produce an allylic radical
RH -» R# + H#, while oxygen adds to the double bond to form a diradical.

Alternatively, oxidation is thought to be induced by oxygen in the

singlet-state interposing between a labile hydrogen to form a hydroper-
oxide directly (RH + O2 -> ROOH).
During propagation, the chain reaction is continued by R* + O2 —»
ROO* and ROO' + RH -> ROOH + R* and hydroperoxides, and new
hydrocarbon radicals. The new radical formed then contributes to the
chain by reacting with another oxygen molecule.
Termination occurs when the radicals interact as follows:
R-+ R--H> RR
R00 # + R* -» ROOR (Nonradical products)
ROO- + ROO- -> ROOR + O2
Trace metals, especially copper, catalyze autoxidation by reacting with
hydroperoxides to create new free radicals and initiate new chain reactions.
M+ + ROOH -> RO* + OH" + M2+ (metal ion is oxidized)
M2+ + ROOH -> ROO* + H+ + M+ (metal ion is reduced)
2R00H -» RO* + ROO* + H2O : Net reaction
In order to avoid the autoxidation problem it has become a common prac-
tice in the edible oil industry to construct reaction vessels of stainless
steel. Citric acid is often added as a metal sequestrant to effectively inac-
tivate trace metal ions.
Antioxidants are used to stabilize fats and fat-containing products against
oxidation and thereby prolong their stability and storage time. An antiox-
idant (AH) acts as a free radical trap to terminate oxidation chain reactions:
R* + AH->RH+A*
RO* +AH -> ROH +A*
ROO* + AH -> ROOH +A*
R*+A*->RA
RO* +A* -> ROA
The major food grade synthetic antioxidants used include butylated
hydroxytoluene (BHT), tertiary butylhydroquinone (TBHQ), propyl gal-
late (PG), and 2,4,5-trihydroxybutylophenone (THBP). The structures of
some of the most important synthetic antioxidants are shown below [5]:
 BHA BHT Gallates
Butylated hydroxyanisole Butylated hydroxytoluene Esters of 3,4,5-tri-hydroxybenzoic acid
(a) 2-teritary-4-hydroxyanisol 2,6-ditertiary-butyl-4-methylphenol R = C3H7(Propyl)
(b) 3-tertiary-4-hydroxyanisol = C8H17 (Octyl)
= C12H25(DOdCCyI)

TBHQ THBP Ionox-100 Ethoxyquin

Tertiary butylhydroquinone Trihydroxybutylophenone
2,4,5-trihydroxybutyrophenone

Ionox-201

Structures of some synthetic antioxidants

 The concentration of an antioxidant in a food fat is important for rea-
sons of cost, safety, sensory properties, and functionality, and generally
they are allowed in food products at 0.01 percent level. Substances such
as citric acid, isopropyl acid, phosphoric acid, ascorbic acid, and tartaric
acid are sometimes added as synergists to enhance the effectiveness of
antioxidants.

4.9 Methods of Analysis and Testing

of Fats and Oils
The main organizations that develop or validate methods for fats and
oil analysis include: International Union for Pure and Applied Chemistry
(IUPAC), International Organization for Standardization (ISO), Association
of Official Analytical Chemists (AOAC), American Oil Chemists' Society
(AOCS), American Society for Testing and Materials (ASTM),
Association Francaise de Normalization (AFNOR), British Standards
Institution (BSI), Deustsches Institute fiir Normung (DIN), and the
Federation of Oils, Seeds and Fats Association (FOSFA). In addition,
there is an increasing trend for the various national standard institu-
tions to develop their own standard methods based on the standard
ISO methods; these are generally adopted as official methods.
In the United States most of the analytical and test methods are
described by the AOCS. These well-established test procedures have
afforded an adequate quality assessment of raw materials or end prod-
ucts or both. Selected analytical methods adopted by AOCS for identi-
fication of the type, determination of the composition, detection of
additives, physical properties, and stability of fats and oils, are sum-
marized below. These methods are subject to the use of prescribed
equipment and techniques of sampling and testing as specified by the
AOCS [6].

4.9.1 Identification and compositional

analysis
The following older, well-established methods based on the estimation of
the selected functional groups or calculation of oil or fat contents are still
used to differentiate oils or fats. However, more accurate and fast ana-
lytical methods, such as gas chromatography of fatty acids and the HPLC
of triglycerides have reduced the significance of these older methods.

Saponification number (SN). This is the weight of KOH (in mg) needed
to hydrolyze a 1-g sample of an oil or fat. The higher the SN, the lower
the average molecular weight of the fatty acid in the triglycerides. Some
SN of various oils and fats are presented in Table 4.12 [2].
TABLE 4.12 Iodine (IN) and Saponification
Numbers (SN) of Various Edible Fats
and Oils

Oil/Fat IN SN
Coconut 256 9
Palm kernel 250 17
Cocoa 194 37
Palm 199 55
Olive 190 84
Peanut 192 156
Rapeseed 225 30
Sunflower 190 132
Soya 192 134
Butter 225 30

Acid value (AV). This value is important for determination of free fatty
acids (FFA) in crude and refined oils and fats. It is the number of
milligrams of KOH needed to neutralize the organic acids present in
1 g of oil or fat. FFA is calculated as free oleic acid and reported as a per-
centage. The AV is determined by multiplying percent FFA with a factor
of 1.99.

iodine value (IN). This value measures the unsaturation of the oils and
fats in terms of the number of grams of iodine absorbed per 100-g
sample. The method is applicable to all normal oils and fats not con-
taining conjugated systems. Some IN of various oils and fats are pre-
sented in Table 4.12.

Hydroxyl number (OHN). This number reflects the content of hydroxy

fatty acids, fatty alcohols, mono- and diacylglycerols, and free glycerol.

Color reactions. Some oils give specific color reactions caused by par-
ticular ingredients. The Halphen test for detecting cottonseed oil is one
example. This test estimates the presence of cottonseed oil in vegetable
or animal fats or oils as the result of a pink color formed between the
reagent (sulfur and carbon disulfide) and cyclopropenoic fatty acids
normally present in cottonseed oil.

Composition of fatty acids. The saturated and unsaturated fatty acids

with 8 to 24 carbon atoms in animal fats, vegetable oils, marine oils, and
fatty acids are quantitatively determined by gas chromatography (GC)
after conversion to their methyl ester forms. However, free fatty acid
analysis is also possible by using specially selected stationary solid
phases. A capillary gas liquid chromatographic method is also used to
measure fatty acid composition and levels of trans unsaturation and cis,
cis methylene-interrupted unsaturation of vegetable oils.
Coupled HPLC-GC methods are used for the detection of adulter-
ation of oils and fats. The identification is done by analysis of unsaponifi-
able minor constituents specific to a particular oil or fat as shown below:
Minor Constituent (analysis) Identification
Squalene Olive or rice oil and fish liver oil
Campesterol/stigmasterol Cocoa butter substitutes
Carotene Raw palm oil
y-/P-Tocopherol Corn oil
y-Tocopherol Wheat germ oil
oc-/y-Tocopherol Sunflower oil
y-/5-Tocopherol Soybean oil
Cholesterol Animal fat
Physical tests for identification. Specific density, index of refraction, color,
viscosity, and melting point tests are used to identify fats and oils. The
onset, flow point, and the temperature range over which melting occurs
are indicative of specific numbers in fats. They are determined by stan-
dardized procedures.
The Solid Fat Index (SFI) estimates the percent of solids in a semi-
solid fat on the basis of changes in volume with temperatures. This is
of importance in fat hydrogenation and interesterification processes.

4.9.2 Quality control tests

A number of analytical methods are used for assessing the quality and
deterioration of oils or fat during refining and subsequent storage con-
ditions. These methods are summarized below:

Lipolysis. Free fatty acids (FFA) result from lipolysis (hydrolysis) of

oils and fats. This is determined by the FFA or acid value. The crude
oils and animal fats usually have a FFA content exceeding 1 percent.
The FFA content is lowered to less than 0.1 percent by the refining of
oil or fat.

Peroxide value. The oxidation of oils and fats leads to the formation of
hydroperoxides. The hydroperoxides readily decompose to produce
aldehydes, ketones, and other volatile products, which are character-
istic of oxidation rancidity. The method for determination of peroxide
concentration is based on the reduction of the hydroperoxide group
with HI (or KI) to liberate free iodine, which may be titrated. The
peroxide value is expressed in terms of a milliequivalent of iodine
formed per kg of fat.

Shelf stability test. Shelf life is predicted by the active oxygen method
(AOM). The fat or oil is subjected to an accelerated oxidation test under
standardized conditions so that the signs of deterioration are revealed
within several hours or days. The sample is heated at 97.8°C while air
is blown through it. The AOM value is reported as the number of hours
to reach a peroxide value of 100 meq/kg.

References
1. Kent, J. A., RiegeVs Handbook of Industrial Chemistry, 9th ed., Chapman & Hall,
New York, 1992.
2. Belitz, H. D. and Grosch, W., Food chemistry, Lipids, Chap. 3, Springer, London, 1999.
3. U.S. Census Bureau, 2003, U.S. Fats & Oils Edible Production and Consumption 2003,
2004.
4. Kellens, I. M., Current Developments in Oil Refining Technology, De Smet Group,
Antwerp, Belgium.
5. Akoh, C. C. and Min, D. B., Food Lipids, Marcel Dekker Inc., New York, 1998.
6. Firestone, D. (Ed.), Official Methods of American Oil Chemists Society, 4th ed., AOCS,
Champaign, 1989.