Chapter 5 : Processing and refining edible oils

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Rural vegetable oil production

Large-scale production
Potential side reactions during high-temperature processing
Physical losses
Fat modification processes
Other considerations
Conclusions

Processing can remove the components of edible oils which may have negative
effects on taste, stability, appearance or nutritional value. To the extent possible,
processing should preserve tocopherols and prevent chemical changes in the
triacyglycerols.

Rural vegetable oil production

Rural oil extraction usually occurs near the areas of raw material production. This
provides the smallscale processor with access to raw materials, helps to ensure that
perishable oil crops are processed quickly, and reduces transport costs. For rural
communities and the urban poor, unrefined vegetable oils contribute significantly
to the total amount of oil consumed. Crude oils are affordable to low-income
groups and serve as important sources of  -carotene and tocopherols.

To maintain the quality of the raw material, care is needed during and after the
harvesting of oilbearing fruits that are perishable and susceptible to fat breakdown.
Bruising of fresh palm fruits accelerates lipase activity leading to fat degradation.
Oil-bearing crops such as sheanuts are prone to mould infestation during storage.
This is curtailed by heat treatment: steaming or boiling, coupled with sun-drying to
reduce the moisture content.

Storage. The moisture content of oil seeds and nuts influences the quality of raw
materials over time. In most rural operations, sun-drying reduces the moisture
content of oil seeds to below 10 percent. Adequate ventilation or aeration of the
seeds or nuts during storage ensures that low moisture levels are maintained and
microbial development is avoided. This is important in the storage of groundnuts
which are highly susceptible to aflatoxin contamination through the growth of
Aspergillusflavus. Since aflatoxins and pesticides are not removed by rural
extraction techniques, microbial contamination and the application of insecticides
should be avoided. There is a need for storage practices which are affordable and
available to the small-scale processor. Perishable raw materials such as palm fruits
should be processed as soon as possible after harvesting.
In humid developing countries, the sun-drying of oil seeds with a high moisture
content, such as mature coconut, is slow and inefficient. Such conditions promote
mould growth which results in high free fatty acid levels and poor organoleptic
qualities. Coconut oil for human consumption should be obtained soon after
harvest.

Pre-treatment. The first operation after harvesting involves sterilization and heat
treatment by steaming or boiling, this inactivates lipolytic enzymes which could
cause rapid degradation of the oil and facilitates the pulping of the mesocarp for oil
extraction. "Sterilised" palm fruits are pulped in a wooden pestle and mortar or
mechanised digestor.

Decortication or shelling separates the oil-bearing portion of the raw material and
eliminates the parts that have little or no nutritional value. Small-scale mechanical
shellers are available for kernels and nuts although manual cracking is still
prevalent.

Most oil seeds and nuts are heat-treated by roasting to liquify the oil in the plant
cells and facilitate its release during extraction. All oil seeds and nuts undergo this
treatment except palm fruits for which "sterilization" replaces this operation.

To increase the surface area and maximize oil yield, the oil-bearing part of
groundnuts, sunflower, sesame, coconut, palm kernel and sheanuts is reduced in
size. Mechanical discattrition mills are commonly used in rural operations.

Extraction. In oil extraction, milled seed is mixed with hot water and boiled to
allow the oil to float and be skimmed off. The milled oil seed is mixed with hot
water to make a paste for kneading by hand or machine until the oil separates as an
emulsion. In groundnut oil extraction, salt is usually added to coagulate the protein
and enhance oil separation.

A large rotating pestle in a fixed mortar system can be powered by motor, humans
or animals to apply friction and pressure to the oil seeds to release oil at the base of
the mortar. Other traditional systems used in rural oil extraction include the use of
heavy stones, wedges, levers and twisted ropes. For pressing, a plate or piston is
manually forced into a perforated cylinder containing the milled or pulped oil mass
by means of a worm. The oil is collected below the perforated chamber. A variety
of mechanical expellers have been designed. The pre-heated raw material is fed
into a horizontal cylinder by a wormshaft. By means of an adjustable choke,
internal pressure which is built up in the cylinder ruptures the oil cells to release
the oil.

Dehydration. By boiling in shallow pans, traces of water in crude oil are removed
after settling. This is common in all rural techniques which recognize the catalytic
role of water in the development of rancidity and poor organoleptic qualities.
Pressed cakes. A by-product of processing, the pressed cake, may be useful
depending on the oil extraction technique applied. Cakes from water-extracted oil
are usually depleted of nutrients. Other traditional techniques, for instance, those
used for groundnut and copra ensure that the by-products, if handled with care, are
suitable for human consumption.

Traditional technologies. In many countries, traditional processes for producing

oil are very important, especially among communities which have easy access to
raw oleaginous materials. Traditional processing tends to be environmentally
sound and the skills required are family or group activities, involving women in
particular. In a changing industrial atmosphere, these positive features have been
outweighed by the negative aspects of traditional processing such as small
production capacities, poor economies of scale, high expenditures of energy and
time, and the cost of transporting oils to markets.

Large-scale production

Storage. Many steps in industrial processing find their origin in the traditional
processes. In large-scale operations, oilseeds are dried to less than 10 percent
moisture. They may be stored for prolonged time periods under suitable conditions
of aeration with precautions against insect and rodent infestation. Such storage
reduces mould infection and mycotoxin contamination and minimizes biological
degradative processes which lead to the development of free fatty acids and colour
in the oil.

Oil-bearing fruits such as olive and palm are treated as quickly as possible. Palm is
sterilized as a first step in processing. Adipose tissues and fish-based raw materials
(that is, the body or liver) are rendered within a few hours by boiling to destroy
enzymes and prevent oil deterioration.

Processing. Oilseeds are generally cleaned of foreign matter before dehulling. The
kernels are ground to reduce size and cooked with steam, and the oil is extracted in
a screw or hydraulic press. The pressed cake is flaked for later extraction of
residual fat with solvents such as "food grade" hexane. Oil can be directly
extracted with solvent from products which are low in oil content, that is, soybean,
ricebran and corn germ.

After sterilization, oil-bearing fruits are pulped (digested) before mechanical

pressing often in a screw press. Palm kernels are removed from pressed cakes and
further processed for oil. Animal tissues are reduced in size before rendering by
wet or dry processes. After autoclaving, tissues of fish are pressed and the oil/water
suspension is passed through centrifuges to separate the oil.

Oil Refining. Refining produces an edible oil with characteristics that consumers
desire such as bland flavour and odour, clear appearance, light colour, stability to
oxidation and suitability for frying. Two main refining routes are alkaline refining
and physical refining (steam stripping, distillative neutralisation) which are used
for removing the free fatty acids.

The classical alkaline refining method usually comprises the following steps:

Step 1. 
Degumming with water to remove the easily hydratable phospholipids and metals.

Step 2. 
Addition of a small amount of phosphoric or citric acid to convert the remaining
non-hydralable phospholipids (Ca, Mg salts) into hydratable phospholipids.

Step 3. 
Neutralising of the free fatty acids with a slight excess of sodium hydroxide
solution, followed by the washing out of soaps and hydrated phospholipids.

Step 4. 
Bleaching with natural or acid-activated clay minerals to adsorb colouring
components and to decompose hydroperoxides.

Step 5. 
Deodorising to remove volatile components, mainly aldehydes and ketones, with
low threshold values for detection by taste or smell. Deodorisation is essentially a
steam distillation process carried out at low pressures (2-6 mbar) and elevated
temperatures (180-220°C).

For some oils, such as sunflower oil or rice bran oil, a clear table product is
obtained by a dewaxing step or crystallization of the wax esters at low temperature,
followed by filtration or centrifugation.

The alkaline neutralisation process has major drawbacks, the yield is relatively low
and oil losses occur due to emulsification and saponification of neutral oil. Also, a
considerable amount of liquid emuent is generated. The soaps are generally split
with sulphuric acid to recover free fatty acids along with sodium sulphate and
some fat-containing acid water steam.

In physical refining, the fatty acids are removed by a steam distillation (stripping)
process similar to deodorisation. The low volatility of fatty acids (depending upon
chain length) requires higher temperatures in physical refining than those required
for only deodorisation. In practice, a maximum temperature of 240-250°C is
sufficient to reduce the free fatty acid content to levels of about 0.05-0.1 percent. A
prerequisite for physical refining is that phosphatides be removed to a level below
5 mg phosphorus/kg oil. In the classic refining process, this level is easily achieved
during the neutralisation stage, but special degumming processes may be required
for physical refining of high-phosphatide seed oils. These procedures rely on
improved hydration of phospholipids by intimate contact of the oil with an aqueous
solution of citric acid, phosphoric acid andlor sodium hydroxide, followed by
bleaching (Segers and van de Sande, 1988).

It is unlikely that the mild reaction conditions during degumming and

neutralisation will induce any significant undesirable changes in the oil
composition. On the contrary, several impurities including oxidised components,
trace metals and colouring materials are partially removed by entrainment with the
phospholipids and soapstock. These impurities are further reduced during
bleaching. Neutralisation also contributes significantly to the removal of
contaminants such as aflatoxin and organophosphorous pesticides (Thomas, 1982).
Organochlorine pesticides and polycyclic aromatic hydrocarbons, if present, must
be removed during the deodorisation/stripping stage and by active carbon
treatment. Some loss of tocopherols and sterols during alkaline neutralisation
usually occurs, however, under wellcontrolled conditions (minimising air contact)
this need not exceed 5-10 percent (Gertz, 1988; Johansson and Hoffmann, 1979).

Potential side reactions during high-temperature processing

The possibility of negative effects of high temperatures during deodorisation and

stripping has evoked concern. In several studies, extreme conditions of temperature
and time (even with free access of air) were applied to produce significant
quantitative results. However, the results of model studies should be related to
practical processing conditions. As early as 1967-1979, the German Society for Fat
Research (DGF) defined upper limits for deodorisation conditions [240°C for 2hrs,
270°C for 30 min.] (Fremdstoff-Kommission, 1973; Gemeinschaftsarbeiten, 1992).

Good manufacturing practice also implies the following: the use of stainless steel
equipment; the careful deaeration at < 100°C before heating to the final stripping
temperature; the use of oxygen-free steam; and strict feedstock specifications
(typically: Fe 0.1, Cu 0.01, P S, bleaching earth 5 mg/kg oil max.).

Investigations in which oil was maltreated under extreme conditions (Rossel,

Kochhar and Jawad, 1981; Jawad, Kochhar and Hudson, 1983 a, b; 1984)
determined the effects of temperature (240-300°C) and time (30-180 min.) during
"physical refining" of soybean oil (degummed with phosphoric acid and lightly
bleached, but still containing 20 mg P, 0.35 mg Fe and 0.05 mg Cu per kg oil). A
strong effect of temperature on the formation of trans fatty acids and polymeric
compounds is shown in Figure 5.1. Time also has a significant effect. At 280-
300°C, there was evidence for appreciable inter- or intra-esterification (increase in
the content of saturated fatty acids at the 2-position of the triacylglycerols);
substantial amounts of conjugated fatty acids were formed as well. The shaded
areas indicate the usual range of processing conditions required for physical
refining (270°C for 30 mini 250°C for 1 h; 240°C for 2 h; 220°C for 3 h). Under
these conditions, all changes induced by the high temperature treatment appear to
be relatively minor.

FIGURE 5.1 : Formation of various artefacts in soybean oil under extreme conditions of
heat treatment

Cis-trans isomerisation. One of the most sensitive parameters used to detect

chemical changes resulting from severe processing conditions is cis-trans
isomerisation, especially of linolenic acid. The most complete study in this area
was made by Eder (1982), who investigated the formation of geometric isomers in
various oils on the laboratory, pilot plant and production scales. On a laboratory
scale, with unbleached soyabean oil at 240ºC, the formation of C18:3 isomers
(determined by GLC) was insignificant (less than 1 percent, even after 5 h, against
3 percent at 260°C). The total trans contents (determined by infrared spectroscopy)
for several types of oils deodorised in stainless steel equipment on the pilot plant
scale is depicted in Figure 5.2. The data show a strong effect of temperature,
especially between 240 and 270°C, and confirm the general trend. That is, even for
highly unsaturated oils containing linolenic acid, the formation of trans isomers is
slow under the conditions recommended for industrial deodorisation/physical
refining (for example, 250°C max.). In conclusion, in the temperature range of
240-250°C, the amount of trans fatty acids formed from unsaturated oils is about 1
percent or less per hour. This figure is consistent with the data discussed earlier
(Rossell, Kochhar and Jawad, 1981; Jawad, Kochhar and Hudson, 1983b). Heating
of oils in air, under simulated frying conditions, has led to similar types of
isomerised fatty acids (Grandgirard, Sebedio and Fleury, 1984; Grandgirard and
Juillard, 1987; Sebedio, Grandgirard and Provost, 1988).

FIGURE 5.2 : Trans fatty acid formation during high temperature deodorisation of
various oils

The formation of positional isomers (that is, double bonds shifted along the fatty
acid chain) of linolenic and linoleic acid under deodorisation/physical refining
conditions has not been reported.

Dimensahon and polymensahon. Quantitative data on the formation of polymeric

compounds from bleached soybean oil are included in Figure 5.1 (Jawed, Kochhar
and Hudson, 1983b). Up to about 260°C, their rate of formation appears to be low;
above 260°C, the increase is more rapid. Similar trends were observed by Eder
(1982). A rapid increase of the amount of polymeric triacylglycerols was only
observed at 270°C. Deodorisation of soybean oil on a commercial scale (2 x 51
min at 240°C) resulted in an increase of 0.5 percent to 0.8 percent polymeric
triacylglycerols.

When the temperature was increased to 270°C in one of the deodoriser trays, 1.5
percent polymers was found. This suggests that the content of di- and polymeric
triacylglycerols do not normally exceed l percent by weight in properly refined oils
and fats.

Strauss, Piater and Sterner (1982) carried out toxicological studies on mice fed
concentrates (24 or 96 percent) of dimeric (incl. polymeric) triacylglycerols
isolated from soybean oil that had been deodorised for 3.5 h at 220°C and 1 h at
270°C and contained 1.5 wt percent of dimers. The acute toxicity was found to be
low with an LD 50 above 18 g/kg body weight. Long term administration of the
dimer concentrate (12 months, 15 wt percent of the 24 percent concentrate in the
diet) did not reveal any significant differences compared with the control group.
The absorption of dimeric fatty acids was found to be poor. Therefore, the presence
of small amounts of dimers and polymers in processed oils does not seem to
present a physiological problem.

Physical losses

During deodorisation or physical refining, volatile components are removed from

the oil by the combination of high temperature, low pressure and stripping action
of inert gas (steam). The degree of removal depends on the physical properties of
the components (especially vapour pressure) and on the temperature and volume of
steam passed through the oil. Some physical losses are highly desirable, for
example, the removal of off- flavours, pesticides and polycyclic aromatic
hydrocarbons, if present. Other losses of nutritionally valuable components, such
as tocopherols and sterols, are potentially undesirable.

Quantitative data on the composition of deodoriser distillates and the removal of

various types of contaminants from oils during deodorisation were reported
(Chaudry, Nelson and Perkins, 1978; Larsson, Eriksson and Cervenka, 1987;
Sagredos, Sintra-Roy and Thomas, 1988; Gemeinschaftarbeiten, 1990). During
high temperature deodorisation or physical refining, especially, the concentrations
of organochlorine pesticides (lindane, DDT etc.), if present in the bleaching oil, are
reduced to very low levels.

Polycyclic aromatic hydrocarbons (PAM) have been a reason for concern since
they were detected in some types of crude oils and fats in the 1960s. An example
of this is coconut oil from copra dried with non-purified smoke gases. Depending
upon the number of aromatic rings, polycyclic aromatic hydrocarbons are
classified as either light (3-4 rings) or heavy (5 or more rings). Some of these
compounds have proven carcinogenic properties, for example, benz- -pyrene.
Light polycyclic aromatic hydrocarbons can be removed by deodorisation or
physical refining, whereas heavy polycyclic aromatic hydrocarbons can be
removed only by adsorption onto activated carbon (Chaudry, Nelson and Perkins,
1978; Larsson, Eriksson and Cervenka, 1987). This treatment, which can be
combined with the bleaching process, is effective in reducing the amount of
polycyclic aromatic hydrocarbons to acceptable levels.
Some loss of tocopherols and sterols by evaporation during high temperature
deodorisation and physical refining is inevitable. However, they have higher
molecular masses and lower volatilities than free fatty acids and light polycyclic
aromatic hydrocarbons. Consequently, the losses of tocopherols and sterols need
not be severe if the processing conditions are well-chosen. Extreme conditions
applied in some model studies do induce more drastic effects. Typical results
obtained for soybean oil (Rossell, Kochhar and Jawad, 1981; Jawad, Kochhar and
Hudson, 1984) are illustrated in Figure 5.3. After 2 hrs at 300°C (a drastic
treatment), the tocopherols and sterols almost completely disappeared, whereas the
actual reduction during physical refining at 240°C for 120 min is only about 15-20
percent. The total refining losses (including pretreatment) are about 25-35 percent.
Many investigators report similar data for a variety of oils. The losses tend to be
higher in physical refining than in alkaline refining because of higher stripping
temperatures.

Under extreme conditions, some isomerisation of  -sitosterol can occur and

individual tocopherols ( , ,  ,  ) and sterols may behave differently when
exposed to high temperatures (Jawed, Kochhar and Hudson, 1984). However, these
phenomena are of minor significance under more realistic conditions. The
percentage composition of the tocopherol and sterol fractions remains essentially
unchanged during processing (Gemeinschaftarbeiten, 1990; Jung, Mood and Min,
1989).

For refined oils such as sunflowerseed, cottonseed and rapeseed oil, an upper limit
of 3035 percent loss of tocopherols throughout the entire processing would still
satisfy the generally accepted criterion of oc-tocopherol equivalents/linoleic
acid  0.6 mg/g (eager, 1975). Soybean oil, which is high in  -tocopherol and
consequently well-protected in vitro, is relatively low in  -tocopherol and cannot
reach this ratio.

The,  -carotene in palm oil is another valuable component that needs

consideration in the refining process. Special processes for retention are being
designed. Olive oil and sesame oil are used in unrefined form since a specific taste
is expected by consumers.

FIGURE 5.3 : Reduction of tocopherol (A) and sterol (B) content of soybean oil during
bleaching and severe heat treatment (time = 2 hours)

Fat modification processes

Hydrogenation. Hydrogenation of edible oils and fats has been applied on a large
scale since the beginning of this century. The process is carried out in a three-phase
system (hydrogen gas, liquid oil and solid catalyst) at temperatures ranging from
about 120°C to about 220ºC max. in the final stages of the reaction. The catalyst
consists of small nickel crystallites supported by an inorganic oxide, usually silica
or alumina. After the reaction, the catalyst is filtered off and any traces of residual
nickel are removed in post-refining to a level of about 0.1 mg/kg or below.

Hydrogenation is a series of consecutive reactions following pseudo first order

reaction kinetics:

K3 K2 K1  
18:3-----> 18:2------> 18:1------> 18:0

in which K3, K2 and K1 are the reaction rate constants for linolenic, linoleic and
oleic acid, respectively. The K3 is much larger than K2 and K,. In nearly all
hydrogenations, linolenic acid is transformed into compounds which are less
saturated. Depending upon the reaction conditions, the socalled Selectivity Ratio
(K2/K1) can change significantly; for example, for nickel catalysts it varies from
approximately 10 at a low temperature to 50 or 100 at high temperature. A high
Selectivity Ratio implies that relatively little saturated acid is formed and that
monounsaturated fatty acids are the dominant reaction product.

Apart from reduction of unsaturation, isomerisation of double bonds also takes

place during hydrogenation: geometric isomerisation (cis-trans) and positional
isomerisation. The mechanisms of hydrogenation and isomerisation are strongly
interrelated (Koritala and Dutton, 1973; Rozendaal, 1976). Initially, a half-
hydrogenated intermediate is formed in which the molecule adsorbed to the
catalyst surface by a single bond can freely rotate. Addition of a second hydrogen
atom results in saturation, whereas abstraction of a hydrogen atom from the half-
hydrogenated intermediate to the nickel surface yields either the original molecule
or a positional or geometric isomer. Hydrogenation of polyenoic fatty acids occurs,
at least partially, through conjugated isomers (for example, c9, t11 or t10, c12)
which are highly reactive and, therefore, rapidly converted into cis or trans
monoenoic acids without accumulating. Of the total amount of trans fatty acids
present in hydrogenated oils and fats, the greater part by far are trans monoenes.
Due to the important role hydrogenation plays in the production of plastic fats,
trans fatty acids may be found in considerable amounts in many products. The
amount of cis,trans and trans,cis dienes is much smaller, whilst the level of
trans,trans dienes seldom exceeds 1 percent. (Gottenbos, 1983).

Apart from hydrogenation, there are two other important fat modification
technologies. The first is interesterification, the random rearrangement of the fatty
acids in the triglyceride molecule under the influence of a moderately alkaline
catalyst. This modifies the melting behaviour of the fat without changing the nature
of the fatty acids. The second is fractionation, the controlled separation of oil/fat
fractions by low temperature (dry fractionation), or solvents (solvent fractionation).
In this process, there are no changes in the chemical nature of the fatty acids. Palm
oil is fractionated into palmolein and palmstearin.
Interrelationships of fat modification technologies. Industry uses various oils and
fats interchangeably while retaining constant quality. Generally, the least
expensive combination of raw materials compatible with the required quality is
chosen. Hydrogenation greatly extends the number of fats available with specified
melting behaviour and this increases interchangeability and lowers costs. In non-
hydrogenation situations, a combination of interesterification, fractionation and
selection of the starting oil may be acceptable solutions for limiting the formation
of isomers in terms of product quality, however, the costs are higher. While the
actual specific modification, for example, hydrogenation or interesterification, is
relatively inexpensive, the costs of losing flexibility can be significantly higher.
The processes for oil modification may change as new compositions become
available through plant biotechnology (Sommerville, 1993).

Other considerations

Storage, transport and packaging of oils. Oils and fats must be protected against
oxidative deterioration, contamination with water, dirt, or other fats, absorption of
foreign odours and tastes, thermal deterioration, and entry of foreign substances
from packaging and lining materials. Temperature, oxygen pressure, oxidation
products, trace metals, oxidative and lipolytic enzymes, reduction in natural
antioxidants and visible and ultraviolet light are all factors in such deterioration.
The use of low storage temperatures, nitrogen or vacuum packaging; the avoidance
of copper, copper alloys and iron as construction material of storage vessels; and
the use of synthetic or natural antioxidants and metal sequestrants as additives,
work to prevent deterioration of oil during storage.

Selection of oil processing technology. The use of oil processing technology and
its application in products is influenced by several factors. For example, the
demand for triacylglycerols with specific fatty acids in the 1, 2 and 3 positions of
the molecule can be met through enzymatic interesterification which uses lipases
as catalysts in the interesterification process. The more readily absorbed fatty acid
in the 2-position can provide for specific triacylglycerols with medical benefits.
For example, essential fatty acids can be supplied to patients with various types of
fat malabsorption or energy can be given to infants with palmitic acid in the 2-
position. Another is the increased use of physical refining because of consumer
pressure for less "chemical" processing.

Conclusions

Rural refining of oil-bearing plants can produce fats and oils of good quality which
provide needed energy and fat soluble vitamins. Commercial refining produces fats
and oils that can be of high quality and have the characteristics of bland taste, clear
colour, good keeping quality and frying stability. Commercially-refined fats and
oils are free from known contaminants extracted from the raw agricultural
products. Refining may remove nutritionally valuable carotenoids to yield oils of
low colour, but retains substantial proportions of tocols, and does not change fatty
acid nor triacylglycerol compositions. Temperature, time and pressure must be
carefully controlled during industrial refining. Oil products should be properly
stored, transported and packaged to maintain quality and consumers must assume
responsibility for not abusing oils and fats within households.

Industry can design almost any fat or oil for a specific application by the use of
various modification processes, such as hydrogenation, interesterification,
fractionation or blending. Hydrogenation typically reduces essential fatty acid
content and creates various fatty acid isomers, both cis and trans. The wide
flexibility available to industry through the selection of raw materials and different
modification processes allows for the production of oils at the lowest cost possible,
an important aspect of food production.