3.
Modifications of Fats & Oils
• Why modification?
• it is desirable or necessary to convert or transform highly unsaturated
refined oils into more saturated forms;
– for greater oxidative stability or altered physical forms of plastic and solid fats
– for physical stability, and functional properties of fats and oils, and their fractions
• Fractionation, interesterification and hydrogenation (hardning) will be
considered
Fractionation
• Fractionation allows the separation of triglycerides of different melting
points or solubility and the gain of one or more stearin or olein fractions
from a fat and oil
• Oils and fats are a mixture of triacylglycerols, i.e., triple esters of glycerol
with different fatty acids.
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Cont’d
• Therefore, fats and oils are not chemically homogenous
substances but a mixture of different triglycerides; hence
– each of these triglycerides has a defined melting point, influencing the physical
properties of the others.
• Fractionation uses this property of fats, i.e., being a mixture of
different substances of the same class.
• This enables one to separate a fat into fractions that are products of
different melting ranges.
• Fractionation is used mainly to improve functionality and/or
improve the commercial value, and to produce special products.
• The oil that is predominantly fractionated is palm oil.
• Palm oil is especially suitable for this technique because of its
composition, i.e, two almost equal parts of saturated and unsaturated
fatty acids that can very easily be separated in to an olein and a
stearin fraction. 2
Inter-esterification
• Inter-esterification of oil changes its molecular composition.
• Oils or fats are mixture of various triacylglycerol molecules having
different fatty acids and positional distribution.
• Treating oils and fats with sodium methoxide as a catalyst at 80 ˚C
causes intermolecule ester exchange, changing the molecular
composition, while leaving the fatty acid composition unchanged.
• As a result, the oil changes its physical properties such as melting
point and consistency.
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Cont’d
• Eg. Improvement of natural lard (pig fat).
• Natural lard tends to form a rough crystal, which is difficult to handle,
during storage. This is because 64% of palmitic acid is attached to 2nd
position of triacylglycerol molecules.
• Randomizing the positional distribution of fatty acids of natural lard by
interesterification improves its physical property, making it a smooth
“rearranged lard”.
• Another example of interesterification is in the field of margarine
production.
• Interesterification of soybean oil and completely hydrogenated
soybean oil provides a material for margarine. This rearranged oil has
an advantage that it does not contain trans fatty acid, because it is
not made through partial hydrogenation.
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Inter-esterification of triacylglycerol molecules
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Fatty acid distribution is randomized, resulting in the change of the physical property of the oil
Cont’d
• Two types of inter-esterification are available, i.e. chemical and
enzymatic.
• In the food industry, intere-sterification can be carried out using a
chemical catalyst or an enzyme.
• Sodium methoxide is generally used as a catalyst in chemical
esterification, while lipases are used in enzymatic esterification.
• Chemical inter-esterification is a random reaction while enzymatic
inter-esterification can be random or regiospecific.
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Comparison of interesterification methods
Chemical interesterification Enzymatic interesterification
1. Low processing cost (batch High processing cost (continuous
reactor) plug-flow reactor, lipase)
2. High processing loss (oil Minimum processing loss
saponification)
3. Low oxidative stability (tocopherol No change in oxidative stability
loss)
4. High levels of reaction by-products Low levels of reaction by-products
(MAG, DAG, glycerol)
5. Flavor reversion problem No flavor reversion
6. Highly reproducible and easily More complex operation and control
controlled
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Hydrogenation
• Hydrogenation is the process of adding hydrogen to unsaturated fatty
acids to reduce the number of double bonds. The purpose of
hydrogenation is twofold:
– To convert liquid oils to semisolid or plastic fats
– To increase the thermal and oxidative stability of the fat, and thus the
shelf life
• Hydrogenation of unsaturated fatty acid occurs when hydrogen gas is
reacted with oil under controlled conditions of temperature and pressure,
and in the presence of a nickel, copper catalyst.
• As the reaction progresses, there is a gradual production of trans fatty
acids that increases the melting point of the fat or oil and creates a more
solid product
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Cont’d
• A typical example of hydrogenation is in the process of margarine and
shortening production.
• Vegetable oil is hydrogenated with gaseous H2 in the presence of a metal
catalyst (usually nickel catalyst).
• If the hydrogenation is completely performed, all the double bounds are
converted to the saturated ones with the same carbon number.
• For example, complete hydrogenation of linoleic acid (18:2-6) generates
stearic acid (18:0).
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Cont’d
Hydrogenation
Complete hydrogenation of linoleic acid, giving stearic acid
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Cont’d
• Vegetable oil is too soft for margarine or shortening because it is liquid.
• Saturated fat obtained by complete hydrogenation is too hard.
• Margarine requires something in the middle, i.e. not too hard and not too
soft.
• Margarine and shortening makers “partially hydrogenate” their product.
• They only add hydrogen atoms until the oil is at the desired consistency.
• When they stop the incomplete hydrogenation process, unsaturated fatty
acids are in varying stages of hydrogenation.
• Some molecules are mostly hydrogenated, while others are not. And the
double bonds have often shifted to unnatural positions, resulting in the
generation of trans fatty acids or trans fat, which is thought to increase risk
of coronary heart disease.
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