INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

Interesterification
It is of common knowledge that natural fats do not have a perfect distribution of fatty
acids among the glyceride molecules. The tendency for certain acids to be more
concentrated at particular Sn positions varies according to species and their
environment and location in the plant or animal. The physical characteristics of a fat
are greatly affected not only by the nature of constituent fatty acids (i.e. chain length
and unsaturation) but also by their distribution in the triacylglycerol molecules. In
effect, the unique fatty acid distribution patterns of some natural fats limits their
industrial applications. Interesterification is one of the processes that can be applied to
improve the consistency of such fats and to improve their usefulness. This process
involves rearranging the fatty acids in such a way that their distribution among the
triacylglycerol molecules of the fat becomes random (random interesterification) or
conforms to some special pattern (directed interesterification).
1. How does interesterification occur?
The term interesterification refers to the exchange of acyl radicals between an ester
and an acid (acidolysis), an ester and an alcohol (alcoholysis) or an ester and an ester
(transesterification). It is the latter reaction that is relevant to the industrial
interesterification of oils (also referred to as randomization) since it involves ester
interchange within a single triacylglycerol molecule (intraesterification) as well as
ester exchange among different molecules.
If one considers that two (n) fatty acids (A and B) are available to be esterified to
glycerol, eight possible triacylglycerol species can result (n3).
Regardless of the distribution of the two acids in the original fat (e.g. AAA and BBB
or ABB, ABA, BBA), interesterification results in the "shuffling" of fatty acids within
a single molecule and among triacylglycerol molecules until an equilibrium is
achieved in which all possible combinations are formed. Quantitative proportions of
the different species depend only on the amount of each acid in the original fat and
can be predicted.
2. Industrial interesterification processes

INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

Batch processes
The most common industrial interesterification process is a batch process using
sodium methanolate or ethanolate as the catalyst. It employs a reaction vessel with
a conical bottom that can be heated, agitated and evacuated. Because alcoholates
react with water and FFA, the oil or fat to be interesterified must be dried to a
water content below 0.01% and neutralized to a FFA content below
0.05%. In practice this is achieved by the addition of caustic soda followed by
drying and taking a sample to demonstrate alkalinity. Drying can be effectively
achieved by spray drying in vacuo, but agitating a batch heated to 80 to 100C or
higher under vacuum and/or sparging with nitrogen is also sufficiently effective.
An amount of 0.05% by weight of catalyst generally suffices and the use of
preweighed aliquots packaged in sealed plastic bags is recommended. Equilibrium
is generally reached within a few minutes at temperatures around 90C but reaction
times of 30 min are common.
After this period of time, the catalyst is inactivated by the addition of water that
may have been acidified. This water leads to the formation of soaps that can
subsequently be removed by washing with water or by the addition of some silica
hydrogel. If acidified water is used for the inactivation, the resulting FFA will be
removed during the subsequent deodorization treatment, which will also remove
the FAME formed after catalyst addition. The yield loss involved in the formation
and subsequent removal of FAME and FFA has been estimated by Kellens (2000)
to amount to 13 times the weight of the sodium methanolate added; this
corresponds to 30% of the variable costs.
According to the enolate mechanism, anhydrous catalyst inactivation would avoid
a fatty acid moiety to be split off and lost. Accordingly, the use of gaseous carbon
dioxide, but the use of phosphoric acid is also mentioned as a means to minimise
process losses; Eckey used glacial acetic acid for catalyst inactivation. Instead of
alkali alcoholates, alkali metals can also be used as catalysts in the randomisation
process. They can be extruded into the oil to be interesterified, where they melt if
the oil is sufficiently warm so that they can be easily dispersed by a homogeniser
or high shear agitator.

INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

Continuous processes
Continuous processes only lend themselves to standard grades with a steady and
sufficiently large demand. Failing this, the necessary product changes would make
the continuous process more expensive than the batch process. Directed
interesterification processes as used for lard in the U.S. were continuous or
semicontinuous. One of the processes used for sunflower seed oil in Belgium
commenced continuously with drying the oil and dispersing the catalyst into the
oil, activating the catalyst, then chilling the interesterifying stream while feeding
this stream into one of several crystallisation vessels, but subsequently, the
contents of these vessels were treated as separate batches. Their temperature was
maintained and controlled by circulating the vessel contents over a scraped surface
heat exchanger and crystallisation was also promoted by slowly agitating the
vessels. When a batch had reacted sufficiently, the catalyst was inactivated by the
addition of water that had been acidulated with phosphoric acid while the vessel
contents were being transferred to a washing vessel. There the reaction mixture
was heated and fully melted, the acid water was drained away, and the oil was
washed with water before being dried and sent to intermediate storage. The review
by Going (1967) shows flow diagrams of continuous randomisation processes
using sodium hydroxide catalyst and sodium methanolate as catalysts. These
diagrams have been redrawn by Rozendaal (1997). Both diagrams show an oil
heater to raise the oil temperature to 150 to 180C and a two-stage vacuum dryer,
but if sodium hydroxide is used, this catalyst is added before the oil is dried. The
hot oil is then given a residence time of 2 min before being cooled, water-washed,
and centrifuged to eliminate the soaps. If sodium methanolate is used as the
catalyst, the oil is dried and cooled to 50C before catalyst addition. The catalyst is
slurried in a small amount of dry oil and metered into the main stream of dry oil,
which is then given some residence time before the catalyst is inactivated by water
addition. The latter process is still being used. In this process, a solution of caustic
soda in glycerol is metered into a stream of preheated oil and the mixture is
sprayed into a vacuum dryer. From this vessel, the reaction mixture is pumped
through a plug flow reactor to the refining stage.\

INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

Process control
In industrial practice, control of the interesterification process amounts to verifying
if the reaction has taken place. If this is not the case, the batch concerned has to be
reprocessed, which means that the control method has to be fast and preferably
suitable for immediate use on the shop floor. If the melting point of the
interesterified product is sufficiently different from the melting point of the starting
mixture, determining the melting point is a quick and easy way of establishing
interesterification. If the difference is fairly small, a fast determination of the solid
fat content may have to be used. In both cases, samples should be taken before
catalyst inactivation so that the reaction can be completed by the addition of extra
catalyst. A quite different approach has been described by Liu and Lampert (1999;
2001). It makes use of the reddish-brown colour that appears on initiation of the
interesterification reaction, since they claim that there is a direct correlation
between the absorbance of the reaction mixture and the degree of
interesterification. Accordingly, they also claim partially interesterified mixtures,
which they say have unique functional properties compared to the physical and
randomized blends. However, they are not that unique since it was shown on
mathematical grounds that partially interesterified products can be regarded as
mixtures of the noninteresterified starting material and the fully randomised endproduct.
3. Mechanisms
There are two proposed mechanisms for interesterification, both important.
Enolate Ion Formation: - This mechanism supports that an enolate ion (II), typical of
the action of a base on an ester, is formed. The enolate ion reacts with another ester
group in the triacylglycerol molecule to produce a -keto ester (III) which in turn
reacts further with other esters to give other -keto esters. In this way all ester groups
may react and in the triacylglycerol will thus move around from their initial positions.
The same mode of action applies to ester interchange between two or more
triacylglycerol molecules. The intra-ester ester interchange is believed to predominate
in the initial stages of the reaction.
Carbonyl Addition: - Here, the alkylate ion adds on to a polarized ester carboxyl
producing a diglycerinate intermediate.
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INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

This intermediate reacts with another glyceride by abstracting a fatty acid, thus
forming a new triacylglycerol and regenerating a diglycerinate for further reaction.
Ester interchange between fully saturated S3 and unsaturated U3 molecules is shown
below, as a model for the randomisation which occurs:
The K values presented are the statistical values of equilibrium constants.
4. Directed Interesterification
A random distribution is not always the most desirable. Interesterification can be
directed away from randomness if the oil is maintained at a temperature below the
melting point of some triacylglycerols which might result. This results in selective
crystallization of the trisaturated glycerides, with the effect of removing them from the
reaction mixture as they crystallize upon formation and the fatty acid composition of
the liquid phase keeps changing. Interesterification thus proceeds with the formation
of more trisaturated glycerides than would have otherwise occurred. The process
continues until most of the saturated fatty acids in the oil have precipitated. If the
original oil is a liquid one containing a substantial amount of saturated acids, it is
possible, by this method, to convert the oil into a mixture of products, one of them a
very unsaturated oil, the other a solid fat with the consistency of shortening, obtained
without resorting to hydrogenation or blending with a hard fat. The procedure is
relatively slow due to the low temperature used, the time required for crystallization,
and the tendency of the catalyst to become coated. A dispersion of liquid sodiumpotassium alloy is commonly used to slough off the coating as it forms.
Rearrangement can also be selectively controlled during interesterification by adding
excess fatty acids and continuously distilling out the liberated acids that are highly
volatile. This impoverishes the fat of its acids of lower molecular weight. The content
of certain acids in fat also can be reduced by using suitable solvents to extract
appropriate acids during the interesterification process.
5. Interesterification products

INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

Several interesterification products have already been mentioned, such as the
interesterified lard produced in the U.S. by randomisation or by directed
interesterification, health margarines produced by directed interesterification of
high linoleic acid oils and the products made by enzymatic interesterification, such
as cocoa butter equivalents, fat bloom inhibitor, and infant. Accordingly, this
section will be limited to interesterification products obtained by chemical
randomisation and used, for example, as hard stock in fat blends for margarines
and shortenings. One such hardstock is based upon palm oil and/or palm stearin
and a lauric oil. Palm stearin itself is not suitable as a hardstock because of its high
content of high melting, fully saturated triglycerides that would give the resulting
spread a sticky feel in the mouth. Accordingly, the melting point of the high
melting triglycerides is reduced by the introduction of shorter chain fatty acids
originating from the lauric oil. Such randomised hardstocks have the additional
advantage that they have not been subjected to the chemical hydrogenation
process, which in health stores tends to be regarded as a positive sales argument.
Their disadvantage is that their use leads to margarines with a relatively high
content of saturated fatty acids. This content has been somewhat reduced by
interesterifying a very hard palm stearin and a palm kernel stearin. The
disadvantage has been more effectively overcome by the use of fully hydrogenated
and randomised blends of a long-chain oil like soya bean oil and a lauric oil, as had
already been described by Gooding (1943). Although the hardstocks themselves
are fully hydrogenated, only small amounts (8 to 15% by weight) are required to
provide tub margarines with the consistency required. Blending a relatively small
amount of such fully hydrogenated hardstocks with, for instance, liquid sunflower
seed oil, allows health margarines to be produced with a fat blend that has a low
(around 25%) content of saturated fatty acids and a relatively high (about 55%)
linoleic acid content. These figures can be improved upon by using the midfraction
of such interesterification. The SFC values of such products have been tabulated by
Allen (1996). In Europe, sunflower seed oil has a health connotation, so spreads
based solely on sunflower seed oil tend to command a premium. However,
partially hydrogenated sunflower seed oil is -tending, so blending this hardstock
with liquid sunflower seed oil will lead to sandiness resulting from the large and
high melting -crystals. This can be effectively overcome by interesterifying the
partially hydrogenated sunflower seed oil with some liquid oil and using the
interesterification product as hardstock to be blended with liquid sunflower seed
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INDUSTRIAL PRODUCTION OF INTER-ESTERIFIED PRODUCTS

oil. Another possibility is to interesterify the partially hydrogenated sunflower seed
oil with oil that is relatively rich in Palmitic acid so that the interesterification
product contains more than 10% of this acid. However, since the hydrogenation
involved is partial, the hardstock and, thus, the final product will contain some
trans isomers, which nowadays are considered to be a disadvantage. They can be
produced by interesterifying fully hydrogenated oil with liquid oil and using the
resulting interesterification product as hardstock. However, when processed, such
fat blends tend to be -persistent, causing the resulting margarine to be somewhat
more brittle and less unctuous. This problem can be alleviated by the addition of
crystallisation accelerators, such as triglycerides having fatty acid carbon chains of
different chain lengths. Finally, fat substitutes, such as olestra, sucrose esterified
with six to eight fatty acids, caprenin (caprocaproylbehenin), salatrim (acronym for
short- and long chain acyl triglyceride molecules), and EPG (esterified
propoxylated glycerin) should also be mentioned as interesterification products. It
does not contribute to the energy content of crisps fried in this fat substitute.
Sorbestrin is the sorbitol equivalent of olestra and is also synthesised by
interesterifying a sugar (sorbitol) with FAME. The EPG fat substitute is also
manufactured by interesterification with FAME. The interesterification substrate is
prepared by allowing propylene oxide to react with glycerol in the presence of an
alkali metal alcoholates catalyst, and the same catalyst is used for the
interesterification with FAME.