FATS AND OIL

LIPIDS:

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

Definition & Composition of Fats

Fats: A triglyceride molecule of fat: 3 fatty acid molecules connected to (or esterified) a
glycerol molecule. The structure of fatty acids determines the properties of fats (ex.
solid/liquid state in room temperature).

Fats, oils and waxes are the naturally occurring esters of long straight-chain
carboxylic acids. They belong to the Saponifiable group of lipids.
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 in an unbranched chain of twelve to twenty four carbon atoms. The
triesters of glycerol fats and oils are also known as triglycerides.

The difference between fats and oils is merely one of melting point: fats are solid at
room temperature (20C) while oils are liquids. Both classes of compounds are
triglycerides.
Since 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 due to the length of the hydrocarbon chains of the acids and the
number of position of double bonds (unsaturation).
The hydrocarbon chains of the fatty acids may be completely saturated (a saturated
fat) or may contain one or more double bonds. The geometric 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 polyunsaturated. The presence of a double bond puts
a kink in the regular zig-zag arrangement characteristics of saturated carbons.
Therefore, the molecules cannot form a neat, compact lattice and tend to coil, so
unsaturated triglycerides often melt below room temperature and are thus classified
as oils.

IMPORTANCE OF FATS & OILS:

Fats and oils are the most concentrated source of energy. They provide
approximately 9 Kcal of energy per gram, compared to 4 Kcal/g for proteins and
carbohydrates. They are carriers of fatsoluble 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.

WAXES:
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.

Plant waxes are usually found on leaves or seeds (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 (C 26H53OH). In addition to
primary alcohols, esters of secondary alcohols, e.g., esters of nonacosane-15-ol are
present:
H 3 C -(C H 2 ) 1 3 -C H -(C H 2 ) 1 3 -C H 3
Waxes can be classified according to their origins as naturally occurring or
synthetic. The naturally occurring waxes can be classified into animal, vegetable
and mineral waxes. The vegetable waxes include carnauba, ouricouri and candelilla.
Petroleum waxes are the most prominent mineral waxes. Paraffin wax is petroleum
wax consisting mainly of normal alkanes with molecular weights usually less than
450.

FATTY ACIDS:
Fatty acids: chains of 4 28 carbon atoms with the carbon chain joined by single or
double bonds, depending on the number of hydrogen atoms attached. Saturated
and unsaturated fatty acids. The acid portion of a fatty acid (FA) is represented by
COOH.
If a FA contains a double bond, the H atom/ other group attached to the carbon
atoms involved in the double bond may have different orientation --- as cis or trans

forms (isomers) Cis and trans forms show different geometrical arrangement and
give a fatty acid different chemical and physical properties.

Carboxylic acids obtained from the hydrolysis of a fat or oil. They are the building
blocks of the triglycerides. The fats and oils are often named as derivatives of these
fatty acids. Normal saturated fatty acids have a long, linear hydrocarbon chain
having a general formula CH3(CH2)nCOOH (where n is even= 2 to 24).The
unsaturated fatty acids may have one double bond (monosaturated) or have more
than one cis- methylene double bond (polyunsaturated).

NAMING OF FATTY ACIDS:

The following three systems of nomenclature are in use for naming fatty acids.

The common (trivial) names.

The number of carbon atoms in the chain.
The International Union of Pure and Applied Chemistry (IUPAC) system.

The trivial names which 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 is from olives.

Abbreviation to designate fatty acids: number of carbon atoms in the

chain, followed by a colon and additional numbers indicating number of double
bonds.
The 18-carbon series:
C18:0 (Stearic acid),
(linolenic acid).

C18:1(oleic acid),

C18:2 (linoleic acid) and C18:3

One or two letter abbreviations are also used, and these four acids sometimes are
designated by St, O,L and Ln, respectively. When double bonds are present, the
suffix anoic is changed toenoic, 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 the 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-octadecenoic, 9,12octadecadienoic and 9,12,15-octadecatrienoicacids, respectively.

Table Some Important Acids, their Names and Common Sources

Carbon Atoms
3
4
5
5
6
8
10
12
14
16
18

Common Saturated
Fatty Acids
Propionic
Butyric
Valeric
Isovaleric
Caproic
Caprylic
Capric
Lauric
Myristic
Palmitic
Stearic

Systematic Name

Common Sources

Propanoic
Butanoic
Pentanoic
3-Methylbutanoic
Hexanoic
Octanoic
Decanoic
Dodecanoic
Tetradecanoic
Hexadecanoic
Octadecanoic

Bacterial fermentation
Milk fats
Bacterial fermentation
Dolphin & porpoise fats
Milk fats, seed oils
Milk fats, Palm seed oils
Ship & goat milk, palm
seed oils, sperm head oil
Coconut-oil
Palm and coconut oils
Palm oil

PHYSICAL PROPETIES 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.

Melting Point The melting range of fats depends on the triglyceride composition.
Melting points increase with chain length. Trans fatty acids always have higher
melting points than their cis counterparts for any chain length. The double bond in
unsaturated fatty acids produces a kink in the chain which means that the fat
molecules cannot pack closely together. As the number of C=C double bonds
increases (amount of unsaturation increases) the amount of kinking increases and
the distance between the fat molecules increases. This decreases the strength of
the van der Waals forces between the molecules, decreasing the melting point.

Melting point data are useful in animal fats and processed fats but are of little value
for vegetable oils since most oils are liquids at ambient temperatures.

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. 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.
Viscosity
Viscosity of the fatty acids increases with chain length and decreases with
increasing unsaturation. There is an approximately linear relationship between log
viscosity and temperature. The viscosity of oils usually increases in prolonged
heating due to polymerization (gum formation).
Density
The density of fats and oils is an index of the weight of a measured volume of the
material. The solid fat index (SFI) is related approximately to the percentage of
solids in a fat at a given temperature. When SFI is determined at a number of
specified temperatures, it can be especially useful to margarine manufacturers or
other processors.
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. The refractive index can be utilized as a control
procedure during hydrogenation processes.
Polymorphism
Polymorphism: the existence of a substance in two or more forms, which are
significantly different in physical or chemical properties. Certain pure or mixed fatty
acid triglycerides may show as many as five different melting points. Each crystal
system has a characteristic melting point, x-ray diffraction pattern and infrared
spectrum. For example, tri stearin can exist in three polymorphic forms with melting
points of 54.7C, 63.2C and 73.5C.Polymorphism has several industrial
implications in use of fats as shortenings, margarines and cocoa butter.
CHEMICAL PROPERTIES OF TRIGLYCERIDES

The most important chemical reactions for triglycerides (fats and edible oils) are
hydrolysis, methanolysis and interesterification. The other reactions: hydrogenation,
isomerization, polymerization and autooxidation.
Hydrolysis
The fat or oil can be hydrolyzed into fatty acids and glycerol by treatment with
steam under elevated pressure and temperature. The reaction is reversible and is
catalyzed by inorganic catalysts (ZnO, MgO or CaO) and an acid catalyst (aromatic
sulfonic acid).

CH2OCOR

CH2OH

CHOCOR + 3 H2O

CHOH

CH2OCOR

CH2OH

+ 3RCOOH

Glycerides can also be hydrolyzed by treatment with alkali (saponification). After

acidification and extraction, the free fatty acids are recovered as alkali salts (soaps).
CH2OCOR

CH2OH

CHOCOR + 3 KOH

CHOH

CH2OCOR

CH2OH

+ 3RCOOK

Methanolysis
The fats and oil reacts 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
CHOCOR + 3 CH3OH
CH2OCOR

CH2OH
RCOOCH3 +

CHOH
CH2OH
+ NaOH
3RCOONa + CH3OH

Interesterification
Interesterification causes fatty acid redistribution within and among triglyceride
molecules. Substantial changes in the physical properties of fats and oils or their
mixtures can be observed without altering the chemical structure of the fatty acids.
The reaction is very slow even at 200-300C, but the rate of reaction can be
accelerated by using sodium methylate.

CH2OCOR1 CH2OCOR2

CH2OCOR2 CH2OCOR1

CHOCOR1 + CHOCOR2

CHOCOR1 + CHOCOR2

CH2OCOR1 CH2OCOR2

CH2OCOR1 CH2OCOR2

etc

Hydrogenation
The unsaturated double bonds in fatty acid chain are converted to saturated bonds
by addition of hydrogen. Suitable solid catalyst: 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).
K1
C 18:3

K2
C 18:2

+H2

K3
C18:1

+H2

C 18:0
+H2

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 100C in the presence of bleaching earths or
catalysts such as nickel, selenium, sulfur or iodine.
Polymerization
Under deep frying conditions (200-300C) the unsaturated fatty acids undergo
polymerization reactions forming dimeric, oligomeric and polymeric 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.
Conjugated fatty acids interact by Diels-Alder reactions producing cyclohexene
derivatives.
Autoxidation
The important lipids involved in oxidation are the unsaturated fatty acid moieties,
oleic, linoleic, and linolenic. The rate of oxidation of these fatty acids increases with
the degree of unsaturation.
Oleic 1 times rate
Linoleic 10 times
Linolenic 100 times
Fats and oils often contain double bonds. Autoxidation of a fat or oil yields a mixture
of products that include low molecular weight carboxylic acids, aldehydes and
methyl ketones. The autoxidation reactions involve three steps: initiation,
propagation, and termination.
Initiation:
RH + O2 -->R + OH
R + O2 --> + ROO

Propagation:
ROO + RH --> R + ROOH
ROOH--> RO + HO
Termination:
R + R --> RR
R + ROO--> ROOR
ROO + ROO --> ROOR + O2
Where RH is any unsaturated fatty acid; R is a free radical formed by removing a
labile hydrogen from a carbon atom adjacent to a double bond; ROOH is a
hydroperoxide, one of the major initial oxidation products that decompose to form
compounds responsible for off-flavors and odors.
Such secondary products include hexanal, pentanal, and malonaldehyde.
The initiation step leads to the formation of a hydroperoxide on a methylene group
adjacent to a double bond; this step proceeds via a free-radical mechanism. 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.
OO
H abstraction
-----CH2---CH=CH-------CH---CH=CH--- + O2
----CH---CH=CH--OO
H
-----CH---CH=CH--- + -----CH---CH=CH---

[-----CH2---CH=CH--- ]

The chain length of these two radical-reaction steps is about100. When the radical
concentration has reached a certain limit, the chain reaction is gradually stopped by
mutual combination of radicals, the termination step.

Measurement of lipid oxidation

Peroxide value
Peroxides are the main initial products of autoxidation. They can be measured by
techniques based on their ability to liberate iodine from potassium iodide, or to
oxidize ferrous to ferric ions. Their content is usually expressed in terms of
milliequivalents of oxygen per kilogram of fat. Although the peroxide value is
applicable for following peroxide formation at the early stages of oxidation, it is,
nevertheless, highly empirical. The accuracy is questionable, the results vary with
details of the procedure used, and the test is extremely sensitive to temperature
changes. During the course of oxidation, peroxide values reach a peak and then
decline.
Thiobarbituric acid (TBA)
TBA is the most widely used test for measuring the extent of lipid peroxidation in
foods due to its simplicity and because its results are highly correlated with sensory
evaluation scores.
The basic principle of the method is the reaction of one molecule of malonaldehyde
and two molecules of TBA to form a red malonaldehyde-TBA complex, which can be
quantitated spectrophotometrically (530nm).

However, this method has been criticized as being nonspecific and insensitive for
the detection of low levels of malonaldehyde. Other TBA-reactive substances
(TBARS) including sugars and other aldehydes could interfere with the
malonaldehyde-TBA reaction. Abnormally low values may result if some of the
malonaldehyde reacts with proteins in an oxidizing system. In many cases, however,
the TBA test is applicable for comparing samples of a single material at different
states of oxidation.
Iodine Value
Iodine value is a measure of the unsaturated linkages in fat and is expressed in
terms of percentage of iodine absorbed. The decline in iodine value is sometimes
used to monitor the reduction of dienoic acids during the course of the autoxidation.
Antioxidants:
Antioxidants function by interfering with the chain reaction. If the number of free
radicals can be kept low enough, oxidation will not occur.
In order to function well as an antioxidant a molecule must:
React with free radicals more rapidly than the free radicals react with lipid.
The products of the reaction with free radicals must not be pro-oxidant.
The molecule must be lipid soluble.
The free radicals formed by conjugated molecules can exist in many resonant
structures as shown below:

Trace metals especially Cu catalyzes auto oxidation by reacting with hydroperoxide

to create new free radicals and initiate chain reaction.
M+ + ROOH
M2+ + ROOH
2ROOR

RO + OH- + M2+
ROO + H+ + M+
RO + ROO + H2O

Citric acid effectively inactivate trace metal ions

R + AH
RH + A
RO + AH
ROH + A

ROO + AH
R+A
RO + A

ROOH + A
RA
ROA

Combinations
Antioxidants are usually combined to take advantage of their differing properties.
For example BHA may be combined with PG and citric acid. The citrate chelates
metals, the propyl gallate provides a high level of initial protection while the BHA
has good carry through properties.
Reasons for Combinations
Take advantage of different properties
Allow for better control and accuracy
May provide synergistic effects
Combinations may provide more complete distribution in some foods
More convenient to handle
Natural Antioxidants
Should not cause off flavors or colors
Must be lipid soluble
Must be non toxic
Should have carry through properties
Must be cost-effective
Examples: Sesame contains sesamol. Reported to be more effective in lard than
BHA or BHT.

Oats have been recognized to have antioxidant properties. Over 25

phenolic compounds have been identified in oats. Many derived from
caffeic and ferulic acid.
Alternatives to Antioxidants
Elimination of oxygen
Packaging under nitrogen;
packaging in vacuum;
packaging with an oxygen scavenger
Elimination of the sensitive substrate
Replacement of polyunsaturated oils with less unsaturated oils, such as olive
oil or palm oil, that are more stable
Decreasing the rate of oxidation
Storage at low temperatures;
storage in the dark;
use of fats and oils that contain low levels of oxidation promoters (e.g.
oxidized products and heavy metals);
use of ingredients that are naturally rich in antioxidants
OILS AND FATS PROCESSING AND REFINING
Crude fats and oils consist primarily of glycerides. They also contain many other
lipids in minor quantities. Corn oil, for example, may contain glycerides plus
phospholipids, glycolipids, manyisomers of sitosterol and stigmasterol (plant
steroids), several tocopherols (vitamins E), vitamin A, waxes, unsaturated
hydrocarbons, as well as many products 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 non-glyceridic co-constituents like:
fatty acids,
partial glycerides (mono- and diglycerides),
phosphatides,
sterols,
hydrocarbons,
pigments (gossypol, chlorophyll), vitamins (carotene),
sterol glucosides, protein fragments, traces of pesticides and heavy
metals.

The general methods employed to produce edible oils suitable for human
consumption consist of:
(a) Seed preparation
(b) Extraction
(c) Degumming
(d) Neutralization
(e) Bleaching
(f) Deodorization
(g) Hydrogenation and sometimes winterization.
Seed Preparation

Seeds Cleaning
When oils seeds, which are received at the oil mill, contain plant residues, damaged
seeds, dust, sand, wood, pieces of metal and foreign seeds. The oils seeds are
carefully cleaned of these materials using magnets, screens, and aspirator systems.
The cleaned seeds are dried to remove moisture. Next, the dried oil-seeds are
usually decorticated to remove the hull that surrounds the oilseed meat before
being further processed. Hulls always contain much less oil than do the kernels or
meats.
Seeds Drying
The moisture of seeds often needs to be reduced to minimize degradation in
storage and to enhance the effectiveness of downstream unit operations. For
example, soybeans are often received at 13% moisture and need to be dried to10%
moisture to facilitate hull removal.
Size Reduction
Most seeds require size reduction prior to further processing. Exceptions are canola,
rapeseed, and corn germ, which are already sufficiently small in size. For most
oleaginous materials, they need to be broken into pieces 2 to 3 mm across to
enhance the downstream unit processes of hull removal, heating/drying, and
flaking.
Hull Removal

Soybeans, sunflower seeds, and delinted cottonseed have a course outer seed coat
known as a hull. The hull fraction is high in fiber content and low in oil and protein
content. Soybeans, sunflower seeds, and delinted cottonseed often have a large
portion of their hull fraction removed so that the finished meal fraction will be
higher in protein by weight, and therefore higher in value.
The process of removing the seed coat of soybeans is commonly referred to as
dehulling, and the process of removing the seed coat from sunflower seeds and
delinted cottonseed is commonly referred to as decortication.
Heating /Drying
All oil extraction processes require that the seeds be heated and sometimes further
dried before oil extraction. In order to enhance the downstream unit operation of
flaking, oleaginous materials are typically heated in the range of 6075 oC
temperature. By heating and softening the oleaginous materials, it enables the
oleaginous material to stretch and flatten in the flaking operation with a minimum
of fragmented particles being created.
For seeds being prepressed prior to solvent extraction, they are typically heated in
the range of 90110oC temperature to decrease the viscosity of the oil and allow the
prepress to expel the oil and make a good quality cake. Materials that are full
pressed are often heated to temperatures of 110150 oC temperature, and dried to
as low as 3% moisture.
Oil expressed without heating contains the least amount of impurities and is often of
edible quality without refining or further processing. Such oils are known as colddrawn, cold-pressed, or virgin oils. The expressed oil from cooked seeds contains
greater quantities of non glyceride impurities such asphospholipids, color bodies
and unsaponifiable matter. Such oils are more highly colored and are not suitable
for edible use.
Flaking
Most seeds are flaked prior to solvent extraction. Flaking distorts the cellular
structure of the oleaginous material and reduces the distance that solvent needs to
penetrate to reach the oil in the seed cells.

EXTRACTION
Most oilseeds are grown specifically for processing to oils and protein meals. The
purpose of oil extraction is twofold. Firstly is to extract the maximum amount of
good quality oils and then to get maximum value from the residual press cake or
meal.
The following three methods, with varying degree of mechanical simplicity are used:
1. Rendering
2. Pressing with mechanical presses and
3. Extracting with a volatile solvent.
EXTRACTION THROUGH MECHANICAL PRESS:
Expeller pressing is the method of extracting oil with a mechanical press rather than
utilizing a chemical extraction process. There are no solvent (chemical) residues in
oil that has been expeller pressed resulting in a cleaner more pure oil, higher in
natural colors and flavors.
An expeller press is a screw type machine, which presses oil seeds through a caged
barrel-like cavity. The heat-conditioned seed is passed into continuous screw-

presses or expellers. The function of this equipment is to reduce the oil content of
the seed from about 42% (8% moisture basis) to 16-20% mechanically.
Expellers consist of a rotating screw shaft in a cylindrical barrel. The barrel has flat
steel bars mounted edgewise around the inside and spaced to allow oil to flow from
between the bars while retaining the solid material within. Pressure and heat are
developed within the barrel by the rotating screw shaft working against an
adjustable choke at the solids (presscake) discharge end of the barrel. The oil seeps
through small openings that do not allow seed fiber solids to pass through. Some
discharge of very fine solids with the oil draining from the expeller is unavoidable.
These fines are separated from the oil by gravity and filtration, and recycled to the
conditioning stage. Afterward, the pressed seeds are formed into a hardened cake,
which is removed from the machine. Pressure involved in expeller pressing creates
heat in the range of 60-99 C.
Subsequent solvent extraction of the remaining oil is then much more efficient and
economical. The presscake, which may be put through a mechanical breaker and
mechanical extrusion to improve its solvent extraction properties by producing
uniform sized particles, is now ready for solvent extraction.
These, small diameter, porous pieces of presscake (collets) have excellent solvent
extraction properties. Capacity of solvent extraction equipment is significantly
enhanced.
While this method is far healthier for consumers and the environment than chemical
extraction, the temperature levels reached results in some loss of antioxidant
potency.
Expeller pressed oils are the second most common form of oil extraction. Since
some oil is left behind in the seed cake after processing, the manufacturer has less
oil processed per batch and is, therefore, more expensive for companies to produce.
But, this method produces higher quality oil with better color and flavors.
Manufacturers will declare this method on their packaging as an expression of
product quality. Look for Expeller Pressed or Cold Pressed prominently displayed on
the label.
Disadvantages of Screw Press:
1.
The process uses considerable horsepower,
2.
There is considerable wear and maintenance,
3.
It takes many machines for high capacity.
4.
7% or 8% residual oil is left in the solids

Solvent Extraction
Nowadays, oil separation by extraction is the commonest process used in vegetable
oil production. Nearly all vegetable oils, apart from olive oil, are produced in this
way, ultimately appearing on the market in the form of refined vegetable oils.
During extraction, a solvent - normally food grade n-hexane - is used to separate
the vegetable oil from cellular material. In order to ensure that the solvent enjoys
unobstructed access to the interior of the seeds, the cell walls need to be broken
down and diffusion pathways need, at the same time, to be kept short. In order to
achieve this, seed is heated, where necessary, and then pulverized mechanically

before being pressed into fine flakes on cylinder rollers. Protein coagulation and
steam generation during this process help to break down cell walls.
In practice, two extraction processes - percolation and immersion - are used,
both of which share a common feature, in that the solvent (extraction agent) flows
in the opposite direction to the seed (extraction material). Fresh solvent is being
brought continuously into contact with seed from which most of the oil has been
extracted, whilst fresh seed is being brought into contact with heavily oil-saturated
solvent, referred to as miscella. After the extraction process, solvent is separated by
distillation from oil and is then re-used.
The immersion process
The immersion process is used where oil has to be obtained from a matrix that is
not easy to extract, as is the case where there are large amounts of unrefined fibre
in the extraction material.
In the immersion process, the entire quantity of seed from which material is to be
extracted is immersed in solvent. The design of the system means that there are no
forced movements, ensuring that oil-saturated solvent (miscella) is constantly being
exchanged with fresh solvent. The static system therefore needs to be stirred, in
order to balance out any differences in concentration. Stirring inevitably causes
abrasion of the extraction material, so the miscella has subsequently to be filtered
out.
The percolation process
The percolation process, also known as the continuous extraction process, is based
upon the principle of uninterrupted wetting of extraction material. Here, solvent
streams past extraction material, allowing interrupted exchanges between this and
the free-flowing solvent that extracts it. Maintenance of a constant solvent flow
ensures that locally saturated solvent flows away and is replaced by noon-saturated
solvent. This process requires free extraction agent flow within the extraction
material.
The advantage of this procedure is that extraction material is not exposed to
mechanical stress. This process is used mainly where "free" oil has to be extracted.
Any fine particles, such as are inevitably formed during extraction, are filtered out
by seed particles and are thereby prevented from entering the miscella.
WHY SOLVENT EXTRACTION
In the mechanical presses 7% or 8% residual oil is left in the solids considerable
horsepower is used, there is considerable wear and maintenance and it takes many
machines for high capacity.
In comparison, solvent extraction with hexane (the primary solvent used worldwide)
will remove all but about % of residual oil, uses less hp, and requires less

maintenance. It is relatively efficient and reliable, and this is one reason why solvent
extraction is the primary means of separating large tonnages of oil from protein
meal.
Why hexane?
1. Actually, it is not a pure n-hexane but a mix of isomers with very similar
properties sometimes called extraction hexane or commercial hexane.
Hexane has about the best characteristics of the many solvents tried over the
years.
2. With a boiling point of 69C it is a liquid in all but the most extreme climates
of the world.
3. With a fairly high volatility and a low sensible heat of 335 kJ/kg it is relatively
easy to remove from the solids and oil with low energy use.
4. It has an azeotrope, a slightly reduced 61.6C boiling temperature when in
the presence of water or steam and resulting in a vapor coming off at about
95% by weight hexane and 5% by weight water. The azeotrope is convenient
for efficient removal of the solvent from solids (or meal) using direct steam
contact.
5. Hexane has a long record of use without as much irritation of human skin or
the immediate or severe toxicity of many competitive solvents.
6. It does not mix with water, allowing fairly simple processes to keep it in the
system while water passes through the extraction process as moisture in the
seed, meal, oil or air.
7. Hexane has a good and aggressive capability to dissolve and mix with
vegetable oils so that it can wash the desired oils out of a fibrous or solid
material. It is selective and leaves the proteins, sugars and some undesired
gums largely undisturbed in the meal.
8. Last, but not least, hexane has a relatively tolerable odor and a low
tendency to cause discomfort when one is subjected to a brief exposure.
Flammability.
Hexane does have one weakness which is universally mentioned: when hexane
vapor is mixed with air in roughly a range from 1.2% to 7.7% by volume, the
mixture is flammable. Over the last century, many processing plants have had fires
or even explosions which caused serious damage.
The typical percolation extractor is designed to operate at a very slight vacuum of
perhaps -0.4 water (-10 mm water) in an effort to enhance safety. As noted, a
mixture with about 5% hexane in 95% air is in the flammable range, but 5% air

uniformly mixed with 95% hexane is not flammable. Therefore, a slight leak of air
into the pure hexane inside the machine may not usually or quickly result in a fire or
significant explosion hazard, but a slight leak of hexane out of the machine and into
the pure air of the extraction room may more often be possible to ignite and
perhaps cause a more energetic explosion. It is also often true that the interior of a
vessel or machine may not have a source of ignition no spark, gasoline engine,
open flame, etc. whereas the outside environment may be less predictable.
(Caution: read up on safety and discuss the issue with experienced people before
presuming that the shallow understanding of any one simple rule is a guarantee of
safety!)
Other solvents? Hexane has maintained the dominant position as a solvent for the
major plants which extract oil from oilseeds. Every so often the media discusses a
new solvent or means of extraction which may replace solvent extraction with
hexane, but (so far) the existing technology has sufficient virtues to maintain
credibility while it continues to be developed in a competitive market. Widespread
use and familiarity assures that many people and resources will continue to improve
on stubborn problems and optimize the hexane process. There is also the advantage
of well understood industry expectations for performance, the availability of trained
personnel, and established standards for safe use. Any proposed replacement must
exceed hexanes basic advantages and still might be expected to require a lot of
time, development and capital investment to work as well.
It should be noted that other solvents may be required to produce different and
specific products. For example, an alcohol-water mixture is used in an additional
extraction step (after hexane extraction) to produce soy protein concentrate (or
SPC) by removing the sugars from standard soybean meal. Various alcohols,
isohexane, heptane, butane many other solvents have found applications in niche
markets. For the standard oil removal plant, only isohexane an isomer with
properties very close to hexane - has replaced hexane in a significant number of
extraction plants. Hexane is the focus of this article since it is still the highest
volume and most commonly used. Hexane is also costly, and it is considered a
pollutant if it escapes from the process. These are additional reasons to avoid the
escape of hexane from the process.
Five Basic Requirements: To achieve effective removal of oil from most oilseeds
using solvent extraction, we may speak of these basic requirements. All kinds of
extractor require proper preparation of the oilseed to achieve good results and one
often hears the phrase, It all begins in preparation. The first requirement is related
to the preparation area and steps including conditioning, cracking, dehulling,
flaking, perhaps prepressing and expanding:

PREPARATION: The term conditioning means to heat the seed and hold it for
proper time and temperature to soften and rupture oil-bearing cells, make the
seed more pliable to reduce generation of fine dust in flaking, and keep the

extractor warm. Correctly prepared materials have high porosity, a large

surface area and thin flakes (or cell breakage in well designed presses) to
allow rapid penetration by solvent and ruptured oil cells so that solvent can
reach the oil. The material must also allow good percolation the rapid flow
of solvent down through the bed and screen so that the oil can be
transported out of the bed.
Once the seed is prepared into appropriate flakes, collets or cake, it is conveyed to
extraction. Then we have four more requirements:

SOLVENT: A high enough solvent ratio (the ratio of solvent to solids entering
the extractor) and a sufficient number of effective stages of wash. These
stages are to be countercurrent with declining oil concentration until the
final pure solvent wash. A machine with more and better stages can operate
with less solvent input (a lower solvent ratio and less solvent in the miscella)
and lower costs in distillation. Efficient stages keep the miscella in later
stages at the lowest possible oil content so that miscella trapped in particles
going to the distillation tower will not contain much oil.

CONTACT: This requires correctly prepared material and an extractor

designed to be forgiving a design leading to the most effective washing
and drainage with a wide variety of materials, even low quality or damaged
seed. A shallow flake bed helps reduce time at each stage and in final
drainage. It also reduces the weight of the bed above which may otherwise
crush fragile flakes. Specially designed stationary screens provide reliable
flow of miscella and removal of solvent and oil.

TIME: There must be enough time for the dissolving and flow processes to
occur. Time is best utilized if an automatic control keeps the bed at full depth
for maximum extractor volume and time, if the extractor drains rapidly at
each stage and particularly at the final drainage so that time is not wasted, if
the extractor is large enough, and if the material is made more dense
sometimes by use of an expander.

TEMPERATURE: There must be a sufficiently high temperature at the extractor

inlet to allow the entire extractor to operate at or near the boiling point of the
solvent. Extraction consists of dissolving, mixing and flow processes; just like
washing grease off a plate in the sink, it works better and faster when hot.

Temperature is a little more complex topic than most people realize. Because the
extractor is usually designed to operate near ambient pressure (with very slight
vacuum), the boiling point of hexane inside is about 69C. However, because there
is hexane and water held in intimate contact throughout the extractor bed, any
vapor which comes off the bed will be near the azeotrope temperature of about

61.7C and that will be the approximate maximum for operation of the extractor.
Even pure hexane heated to 69C before entry to the extractor will boil some as it
contacts the water in the flake bed. Any such boiling in the bed will reduce drainage
of solvent and hinder extraction. Therefore, the practical result is that the extraction
bed will have a maximum efficient temperature of about 60-66C and it will resist
going to higher temperatures by boiling off a lot of vapor. If material is introduced to
the extractor too hot it will cause a great deal of boiling off of solvent and water
and reduce extraction drainage and reduce extraction efficiency.
Operate Near the Azeotrope! It is difficult to operate above the azeotrope. But it
is very desirable to operate close to 61-63C at all points in the extractor. Operating
at the hottest reasonable temperature makes the solvent and oil as low viscosity as
possible and promotes rapid dissolving, mixing and flow. This allows the fastest
possible extraction and better extraction results. Furthermore, since the extractor is
only designed to operate near ambient pressure, any temperature below the
azeotrope will result in a lot of air in the extractor. If temperature is very low the
elevated air (and oxygen) content could even become a hazard for fire, but usually
it is more of a concern due to internal corrosion of the extractor. Experience shows
that where an extractor is cold inside, it has high air contact and high oxidation of
steel and may eventually cut away enough metal to leak or have some structural
problem.

REFINING OF VEGETABLE OILS

In many local markets further refining is not required as the flavours of unrefined
oils may be readily acceptable. However these stages are carried out in large-scale
operations and for international markets which tend to prefer a less-coloured and
odorless product. Refining has for its object the removal of free fatty acids and other
objectionable substances -- principally nitrogenous and mucilaginous matters.
These refining steps are:

Degumming

Degumming is a way of treating oils that have high phosphatides content. The
phosphatide, which makes a gummy residue, is removed by mixing the oil with 2 or
3 % water. These hydrated phosphatides can then be removed by settling, filtering
or centrifugation.
The crude oil from the two extraction stages is usually blended and then
degummed before being stored for sale or further processing. Degumming removes
phosphatides co extracted with the oil, which tend to separate from the oil as
sludge during storage. The phosphatides content of crude oil varies, but is usually in
the order of 1.25%, or measured as phosphorus, 500 ppm.
Two degumming methods are in use:
(a) Using water to precipitate phosphatides and;

(b) Using an acid such as citric, malic, or phosphoric and water (super degumming).
After contacting the oil with these reagents, the oil is centrifuged to separate the
precipitated material. Degumming with water only, leaves from 100-250 ppm of
phosphorus, depending on the extent of hydrolysis of phosphatides in the course of
seed preparation, as discussed earlier. In degumming with an acid and water, the
hydrolyzed, non-hydratable phosphatides (NHP) are also removed. Residual
concentrations are about 25 ppm of phosphorus. The separated phosphatides are
added to the meal in the desolventizer. This raises the residual oil content of the
meal to about 2-3% and raises its energy content.
The most recent development in degumming uses acid and aqueous sodium
hydroxide, rather than acid and water, especially with lower quality oils. This
represents an intermediate between acid-water degumming and alkali refining.
Phosphatides as well as some of the other impurities are removed and, if sufficient
alkali is applied to saponify the free fatty acids, fully refined oil is obtainable.

Neutralization
Fatty acids can be neutralized by adding a sodium hydroxide solution, also known as
caustic soda, or by stripping, which is a similar process to de-odorizing.
Degummed oil is further purified in a process of refining. One of two methods are
used, namely, alkali refining, especially with water degummed oil, and physical
refining with acid-water degummed oil. Alkali refining is the most common process
used, even with acid-water degummed oil.
Physical refining is a relatively new development. It requires well-degummed oil of
moderate chlorophyll and free fattyacid content, but it is then very economical.
In alkali refining, the oil is first contacted with about0.05-0.1% of concentrated
phosphoric acid in a high intensity mixer to help precipitate phosphatides. It is then
contacted with an approximately 12% aqueous solution of sodium hydroxide to
neutralize the free fatty acids and any excess phosphoric acid present, and to
precipitate phosphatides. This requires about 2-3% of the solution. Very intensive
mixing is used. Temperatures and contact times may vary from about 90C and only
seconds for both acid and caustic in the so called short-mix process to about 40C
and 15 minutes each in the long-mix process. The oil/soap mixture is then heated
to about 90C, if required, and centrifuged to separate the aqueous soap phase.
This phase also contains the precipitated phosphatides and some triglyceride oil.
The centrifuged oil must be further contacted with about 5-10%hot water to reduce
soap levels from about 400 ppm to <50 ppm. Free fatty acids are reduced to
<0.05%and phosphorus to <2 ppm. Iron and copper concentrations are reduced to
below detection. Coloured compounds (chlorophylloids, carotenoids) are not
affected significantly. The concentration of sulfur compounds is reduced slightly.
This oil is now ready for bleaching. The soap phase from this operation can be
added to the meal, similar to the disposal of the phosphatides from degumming, or
it can be acidulated and used as a feed ingredient. The wash water must be treated
to reduce the oil content to acceptable levels for discharge.

In physical refining, acid-water degummed oil with phosphorus content below 50

ppm is first subject to a phosphoric acid pretreatment, as in the short-mix alkali
refining process. It is then contacted with acid-activated bleaching clay in a
standard bleaching process at 95-105C.The clay, along with precipitated
phosphatides and adsorbed chlorophylloid and some carotenoid compounds, is then
removed by filtration. This is the first and most important stage of physical refining.
It delivers bleached oil ready for deodorizing. Except for the free fatty acids in the
oil, all other minor constituents are reduced to the same concentrations as in alkali
refining and in addition, chlorophyll is reduced to the concentration required of
bleached oil, namely <25 ppb. Usually, from 1-3% acid-activated bleaching clay is
used, depending primarily on the concentration and type of chlorophylloid
compounds present in the oil.
The removal of the free fatty acids in the oil is done by steam distillation in a
deodorizer. This simultaneously deodorizes the oil. Because deodorization is the last
process normally carried out on edible oils, this step may be delayed until other
processes, such as hydrogenation of the oil, have been done.
The under layer of soap and other impurities, which is drawn off from the oil,
consists of solid matter mixed with some water. It is known as foots, probably
because it collects at the foot of the tank. A large proportion of it is soap. It may be
sold to soap makers for use in the lower grades of soap, the price being based on
the percentage of fatty acid present in it. Hence it is also known as soap stock. Or it
may be treated with strong sulfuric acid to set free the fatty acids contained in it.
These then float to the surface, are skimmed off, and sold to the soap or candle
maker. This product is known commercially as acidulated foots. It pays to produce it
rather than to sell ordinary foots whenever the freight from the refinery to the soap
maker is considerable, for by converting foots into acidulated foots the weight is
reduced about one-half. A third use for foots is to convert it into washing powder by
mixing with a suitable amount of soda ash.

Bleaching

Some oils have a very dark colour which can be unpopular with consumers. The
appearance of the oil can be lightened by bleaching. Most crude vegetable oils are
deeply colored. They must be bleached. There are many methods, but the one in
most general use in America is to agitate them, after they have been refined, with
some solid material which absorbs the color. The usual material is fuller's earth.
Adsorptive Bleaching
Alkali refined oil, which still contains most of the chlorophylloid compounds present
in the crude oil, requires bleaching. These compounds must be removed. They
catalyze oil oxidation and give an undesirable green colour to the oil.
To the dry oil dry fuller's earth is added, usually only a few per cent, the quantity
depending upon the character of the oil and the temperature; the mixture is then
warmed, usually to less than 80 degrees Centigrade, and agitated for one-half to
one hour. It is then pumped through a filter press which retains the fuller's earth and
permits the oil to run out clear.
It has become recognized that chlorophyll removal is the most important aspect of
oil bleaching. Acid-activated clays are used. Their adsorptive properties are
especially effective for the removal of these compounds. Other coloured

compounds, some of the oxidation breakdown products and traces of iron are also
removed in this process.
The process itself is carried out under vacuum with the oil at about 100C. Many
process versions are in use. About 5-30minutes of contact time is given, while the
oil/clay slurry is progressively dried to about 0.1% moisture content. This gives the
best adsorption efficiency. As indicated earlier, about1-3% clay (10% moisture
content) may be required to achieve chlorophyll removal to <25 ppb. This level is
innocuous inrespect to oxidation and colour of the oil.
An appreciable amount of the oil remains in the earth retained in the press at the
end of the operation. A considerable proportion of this is sometimes recovered by
forcing dry steam through the press which carries out with it much of this residual
oil.

Deodorizing
Volatile compounds that produce odours can be eliminated through the process of
sparging, i.e. bubbling steam through the oil, under a vacuum.
Many oils even after they have been refined and decolorized to transparent
whiteness retain a disagreeable odor and flavor. This is especially true of cottonseed
oil. Such oils may be deodorized by blowing steam through them, since the
substances responsible for odors and flavors are usually volatile. A still more
effective way is to blow the steam through the oil after it has been heated to a high
temperature, say 34OoF. The most effective method is to carry on this treatment in a
vacuum.

Winterization

Allowing the oil to stand for a time at low temperatures so that glycerides, which
naturally occur in the oil, with higher melting points solidify and can then is
removed from the oil by filtering. This step is usually carried out with palm oil to
separate the oil into two separate products: a solid fat (stearin) and liquid oil (olein).
Fats and oils are mechanical mixtures of a number of triglycerides. Now, different
triglycerides solidify and melt at different temperatures. Therefore if oil consists of a
number of triglycerides, some of which remain liquid at low temperatures while
others become solid, and such oil is exposed to a low temperature, more or less
sediment forms consisting of the triglycerides that separate out at that
temperature. Indeed, the oil may be completely converted into a solid cake if it is
cooled down far enough.
Manufacturers, therefore, subject such oils to a process which prevents the
separation of solids in all but the most extremely cold weather. Oil so treated is
known, naturally, as winter oil, and the process is known as winterizing.
Winterizing is a very simple procedure. The oil is very slowly chilled in large tanks
to the temperature at which it is to remain clear. It is allowed to stand quietly at that
temperature for a considerable length of time to permit the separation of the solid
crystalline materials from the liquid to become complete. The oil with the
suspended solid matter is then pumped through filter presses which retain the solid
and allow the liquid to run out. The solid remaining in the press is known as stearin

because largely composed of the glycerides of stearic acid. It is used in soap and
candle making.
Canola oil, very low concentrations of these fatty acids can be achieved with very
little hardening of the oil taking place. Melting behavior is most usually evaluated by
determining the proportion of solid fat in a sample over the temperature range of
interest, usually10-40C.