2.
2 Refining
• Crude oils are not usually considered to be edible until numerous non-glyceride
compounds removed through operations collectively known as refining.
• However, some oils, such as olive, tallow, and lard, have been consumed without
refining.
• Undesirable components of crude oils include
– small amounts of protein or other solids,
– phosphatides,
– undesirable natural flavors and odors,
– free fatty acids,
– pigments,
– waxes,
– sulfur-containing compounds (canola and rapeseed),
– trace solvent residue, and water.
• However, not all non-glyceride compounds are disadvantageous. Tocopherols
protect the oil against autoxidation and provide vitamin E activity, and β-carotene
provides vitamin A activity. 1
Cont’d
• Unfortunately, some of the refining operations are not perfectly selective
and also remove some beneficial compounds along with the targeted
undesirable ones.
• There are two major types of refining: chemical and physical.
• The major steps involved in chemical refining include degumming,
neutralizing, bleaching, and deodorizing.
• Physical refining removes free fatty acids and flavors by distillation
Degumming
• Degumming is a water-washing process to remove phosphatides.
• Unless removed, phosphatides can spontaneously hydrate from moisture in
the air during storage or in the headspace.
2
Cont’d
• Degumming may be conducted either as a separate operation or
simultaneously with neutralization.
• In the cases of oils rich in phosphatides, such as soybean and canola
oils, degumming is usually a separate operation
• Hydration makes phosphatides insoluble in the oil, and they precipitate,
yielding an oil that is unattractive because of unsightly sludge or gums.
• Phosphatides can degrade and cause dark colors when the oil is heated
as in the later deodorization step
• Phosphatides are also surfactants and, if present in frying oils, can
cause dangerous foaming
• Phosphatides, also known as lecithin, are important food emulsifiers and,
in the case of soybean oil, often times become economical to recover
• The gums are rendered insoluble in oil by hydrating them with 1–3%
water
3
Cont’d
• As a general rule, the amount of water should be equivalent to the
hydratable phosphatide content of the oil.
• If single-bleached lecithin is to be recovered, then hydrogen
peroxide may be added to the water;
• if double-bleached lecithin is to be recovered, then benzoyl
peroxide may also be added
• The mixture is intensively mixed and then agitated for 30–60 minutes
at 60–80 0C in a slow mixing vessel (hydration tank) to allow the
phosphatides to become fully hydrated and to coalesce.
• The gums, being more dense than oil, can be removed by settling or
filtering; more often, however, they are centrifuged out.
• The wet degummed oil is either dried or immediately neutralized.
• Usually, about 90% of the phosphatides are removed by this process.
• The gums typically contain 25% water and 75% oil-soluble
substances (of which one-third is neutral oil) 4
Cont’d
• There are both hydratable and non-hydratable phosphatides.
• The phosphatides are composed of phosphatidylcholine,
phosphatidylinositol, phosphatidylethanolamine, and phosphatidic acid.
• The first two are always hydratable; but, the latter two can complex with
divalent metal ions, rendering them non-hydratable.
• Acid degumming and super degumming make more of the
phosphatides hydratable. Nonhydratable phosphatides remain oil soluble.
• Phosphoric acid is added to make the phosphatides more hydratable by
binding calcium and magnesium ions before adding water. Phosphoric
acid pretreatment also partially removes chlorophyll from the oil.
5
Cont’d
• Superdegumming processes have been developed in which more of
the phosphatides are rendered hydratable.
• A strong solution of citric acid is added to warm oil (700C), and the
mixture is stirred and cooled to 250C to precondition the gums. Then
water is added with stirring for an additional 3 hours to hydrate the
gums.
• This process causes the phosphatides to form liquid phospholipid
crystals, which are easily removed during centrifugation.
• Another variation of degumming, dry degumming, is occasionally
applied to oils relatively low in phosphatide content, such as palm,
coconut, and peanut oils.
• The oil is treated with concentrated acid to agglomerate the gums.
The gums are then separated from the oil by being adsorbed to
bleaching earth during subsequent steps of bleaching and filtering
6
Neutralization (Alkali Refining)
• Neutralization is the most important operation in refining edible oils
• Neutralization is achieved by reacting the free fatty acid with caustic
soda (sodium hydroxide) to form soap referred to as soapstock.
• Soapstock is removed from the oil by using continuous, disk-type
centrifuges.
• Neutralization must be done correctly or some of the glycerides will
be saponified, resulting in increased refining loss.
• The oil, low in acid value, is termed neutral oil.
• Removing the soapstock must also be carefully done to prevent high
losses of neutral oil, which is a second means of increasing refining
loss.
• Proper neutralization is dependent upon using the proper amount of
sodium hydroxide, proper mixing, proper temperature, adequate
contact time, and efficient separation.
7
Cont’d
• Refined oil is then washed with soft water (10–20%) at 900C and re-
centrifuged to remove most of the soap.
• The remaining soap is removed during bleaching. The presence of
excessive soap going into the bleaching operation can reduce the
effectiveness in removing colors.
Bleaching
• The primary purpose of bleaching is to improve oil color by removing
pigments with:
– neutral clays,
– activated earths,
– synthetic silicates,
– silica gel, and carbon black.
• Other benefits of bleaching are the breakdown of peroxides and
cleanup of residual traces of soaps and phosphatides 8
Cont’d
• The primary pigments of concern are those that give red-brown
(carotenoids, xanthophyll, gossypol, etc.) or green colors (chlorophyll).
Deodorization
• The final step in refining fats and oils is deodorization.
• The primary objective of deodorization is to remove compounds
responsible for undesirable odors and flavors, such as
– residual free fatty acids (especially low molecular weight fatty acids),
– aldehydes,
– ketones, and alcohols.
– residual pesticide and hexane. Some pigments, such as β-carotene
• Deodorization also removes peroxide decomposition products; freshly
deodorized oil should have a perioxide value of zero and free fatty acid
content of <0.03%.
9
Cont’d
• Deodorization is essentially steam distillation performed at high
temperatures (180–270oC) and under high vacuum (3–8 mm Hg
absolute pressure).
• Factors that affect the efficacy of deodorization are:
– the vapor pressures of the materials to be removed,
– the product flow rate,
– the intimacy of steam mixing with the oil,
– the absolute pressure achieved during deodorization,
– the temperature of deodorization (which controls the vapor
pressure of the materials being removed),
– the sparge steam rate, and the time of deodorization
• Deodorization may be conducted in either batch, semi-batch, or
continuous vessels.
10
Cont’d
• There are five stages in deodorization: deaeration, heating, steam
stripping, heat recovery/cooling, and final cooling.
• After the deodorized oil has cooled, a small amount (0.005–0.01%) of
citric acid is added to chelate metal cations so they would not
promote oxidation and reduce shelf life.
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