Degumming, Refining, Bleaching, and
Deodorization Theory
JOHN C. COWAN, Adjunct Professor of Chemistry,
Bradley University, Peoria. Illinois, USA
ABSTRACT
Basic t h e o r y and principles of degumming,
refining, bleaching, and deodorization are reviewed.
Composition of crude oils, hydration of ions and
molecules, neutralization of organic acid, and sepa-
ration and modification of products by centrifuga-
tion, adsorption, and vacuum steam distillation are
briefly summarized. Reactions of vegetable oils
include hydration, neutralization, and oxidation.
INTRODUCTION
A variety of procedures which include both reactions
and physical separations may be involved in the conversion
of crude vegetable oil to an edible product. The important
reactions are hydration of phospholipids in degumming, the
neutralization of free fatty acids with alkali, and the autoxi-
dation and cyclization of pigments to remove color. Deli-
berate attempts are made to reduce autoxidation to a
minimum, but it usually occurs to the detriment of the oil.
Hydration occurs whenever water is mixed with crude oils
or when free fatty acids are neutralized. More important
than the reactions are the physical separations that occur
by centrifugation in degumming and alkali or other re-
fining, adsorption in bleaching, and vacuum steam distilla-
tion in deodorization.
COMPOSITION
Of primary importance in the refining of any oil is its
composition. Although most fatty materials of similar
origin can be converted to edible products by similar
procedures, the composition of the particular starting
material or crude oil is a determining factor. Some of the
many materials present in a crude oil are triglycerides, free
fatty acids, sterols, tocopherols, phospholipids, pigments,
oxidized products, and waxes.
The triglycerides or triacyl glycerols constitute over 95%
of most crude oils, and they are the material that we wish
to purify. However, we must not do so to the extent of
removing all of the other minor components. Usually, free
fatty acids, phospholipids, pigments to some degree, oxida-
tive products, and waxes are the only materials that need be
removed. Sometimes it is not necessary to be concerned
with pigments, waxes, and oxidation products. The major
concern is usually with free fatty acids and phospholipids.
The amount of free fatty acids present is a measure of
the quality of the unrefined as well as the refined oil. If it is
t o o high, alternate procedures or alternate inedible uses
should be sought.
Free fatty acids are lowered by refining, such as with
alkali, or by other methods. An excess of alkali is added
over the amount necessary to neutralize the free fatty acid
present. The suspension or solution which results is usually
separated by centrifugation. Vacuum steam distillation can
also be used to separate free fatty acids provided the
amounts are not too high and phospholipids are low.
Pigments present in vegetable oils include carotene
(CH), xanthophyll (CHO), chlorophyll (CHNO), gossypol
(polyphenol), chroman-quinone, diketones, and browning
products. Many different materials are included under this
heading, including a-, ~-, and 'y-carotene. These are conju-
344
gated hydrocarbons with isoprene units that will heat
bleach and oxidize readily. Their conjugation imparts an
orange to red color. Oxidation or heating removes this
color. Indeed, oxidation of the central double bond changes
red to yellow color. Xanthophylls are oxygen "analogs" of
the carotenes. Other pigments may assume a major
importance in some oils, e.g., gossypol in cottonseed oil,
chlorophyll in green soybean oil, and a-tocopherol in a
number of oils. a-Tocopherol oxidizes to a very colorful
chroman-quinone. Chlorophyll is better removed before
alkali treatment since chlorophyll tends to be stabilized by
alkali and heat and harder to remove. Oxidation can also
lead to yellow diketones and brown colors.
The phosphatides in oils like soybean oil often receive
special treatment. Their main classes are phosphoglycerides,
p h o s p h o i n o s i t i d e s , and phytosphingosines. The ionic
structrue of phosphatidyl choline and ethanolamine are
shown in Figure 1. These phospholipids are nature's
emulsifiers and find many uses. Their ionic structures
readily hydrate to permit removal by centrifugation.
If waxes are a problem, they are usually removed by
winterization (cooling and filtering).
SEPARATION AND REACTIONS
The primary methods used in separations are centrifuga-
tion as already mentioned in removal of pigments, and
vacuum steam distillation for the removal of oxidative
cleavage products (odors and flavors) and free fatty acids.
Reactions involved include hydration as already mentioned
under phospholipids, neutralization with alkali to form
soaps (acids are sometimes used in refining but will not be
discussed in this paper), and oxidation which should be
avoided but usually occurs in sufficient amounts to bleach
or improve the color of the oil.
Hydration occurs with the ionic part of the phospho-
lipid molecule, but many ions are hydrated in presence of
water. Table I lists some of the ions that may occur in the
hydration and refining of an oil. The hydrogen ion (H +) is
often cited as being H 3 0 +, but it is more likely to be
H904 + or even higher in water.
Oxidation usually occurs between the unsaturated
bonds in the oil to form hydroperoxides. Autoxidation of
oleic ester is shown in Figure 2. Four different hydroper-
oxides are formed. These decompose to form some of the
products shown in Figure 3. The latter also shows some of
the oxidative cleavage that results from autoxidation from
other unsaturated esters. These cleavage products impart
odor and flavor to oils and must be removed by steam
0
t
RCH2OP?CH2 CH2NH3+
O-
Phosphatidyl Ethanolamine (Cephalin)
O
t +
RCH2OP OCH2CH2N(CH3)3
O-
Phosphatidyl Choline (Lecithin)
FIG. 1. Two phospholipids, ionic part only.
J. AM. OIL CHEMISTS' SOC., June 19"/6 (VOL. 53)
 TABLE I RCH2CH=CHCH 2 R Oleate
Hydrated Ions
RCHCH=CHCH2R' Hydro-
Hydrogen Metals I
OOH
H302 + ....................... Na(H20)4 + RCH=CH-~HCH 2 R' Peroxides
H502 + ....................... K(H20)4 + OOH
H703 + ....................... Fe(H20)6
RCH2CHCH=CHR'
H904 + ....................... Mg(H20)62+
OOH
....................... Ni(H20)62+ / OOH
RCH2CH=CHCH-R'

FIG. 2. Autoxidation of oleic ester.

d e o d o r i z a t i o n . A t high t e m p e r a t u r e s , t h e h y d r o p e r o x i d e s
are also d e s t r o y e d .
CH3(CH2)6CHO CH3(CH2)2CHO
CH3(CH2)7CHO CH3(CH2) 3CHO
CENTRI FUGATION
CH 3(CH2)6 CH=CHCHO
The basic t h e o r y for centrifugation is o u t l i n e d in
f o r m u l a s C1-C1 1 below. CH3(CH2)7CH=CHCHO
OHCCH2CHO
F = ma(C1) F = w2r(C2)
F = (M'-m)w2r(C3) F = Force OHC(CH2)2CHO
m' = mass of the particle FIG. 3. Cleavage products.
m = mass of equal volume of liquid
w = angular velocity
r = radial distance e q u a t e t h e s e t w o e q u a t i o n s a n d solve for t h e settling s p e e d
Vs, we have e q u a t i o n C6. T h e v e l o c i t y (Vg), t h e settling
F = Ap YI D3w2r (C4) where speed in a s e t t l i n g t a n k due to gravity, will b e e q u a t i o n C7,
6 w h e r e g is gravity a n d replaces w2r.
If we assume a c e n t r i f u g e b o w l in t h e s h a p e of a cylin-
Ap = difference in density between der w i t h liquid fed c o n t i n u o u s l y i n t o o n e e n d a n d o u t t h e
particle and liquid
o t h e r , t h e liquid will be against t h e wall w i t h a t h i c k n e s s , S.
T h e time, T, d u r i n g w h i c h t h e liquid is in t h e b o w l is V / Q ,
F' = 3YIr/Dv(Stokes Law) (C5)
w h e r e V is t h e v o l u m e in t h e b o w l a n d Q is v o l u m e r a t e of
r/ = viscosity of liquid flow. W h e n t h e t h i c k n e s s is small, t h e d i s t a n c e x s e t t l e d b y
v = speed of particle t h e particle b e c o m e s C8, w h e r e v s c o m e s f r o m f o r m u l a C6
D = diameter of particle a n d V / Q is e q u a l to t as s h o w n in C8.
Half o f t h e particles of d i a m e t e r D will be s e d i m e n t e d
Ap -~6 D3w2r = 31-IDvs a n d h a l f will n o t be w h e n x = S/2. This is k n o w n as 50%
cut-off or s i m p l y c u t o f f . T h e flow Q t h e n b e c o m e s f o r m u l a
ApD2w2r (C6) C9. The first h a l f o f this e q u a t i o n follows S t o k e s Law, a n d
Vs - 18 v
t h e s e c o n d follows t h e p a r a m e t e r s o f t h e r o t o r involved.
Vg = ApD2g gravity T h u s , Q is p r o p o r t i o n a l to 2 t i m e s t h e Vg t i m e s N, w h i c h is
18 n (C7) t h e s u m m a t i o n of t h e p a r a m e t e r s of t h e r o t o r e x p r e s s e d in
f o r m u l a C11.
ApD2W2r . V (C8)
x = Vst = 18"0 -'Q
BLEACHING
t = time V = volume of liquid
Q = volume rate of flow T h e r e m o v a l of t h e e f f e c t o f p i g m e n t s can b e carried o u t
when x = s/2 (cutoff) in several ways:
1. A d s o r p t i o n of p i g m e n t s b y clay, c a r b o n black, or o t h e r
ApD 2 Vw2r suitable material
Q = 9r/ " s (C9)
2. H e a t i n g t h e oil p a r t i c u l a r l y in t h e p r e s e n c e o f o x y g e n or
Q = 2Vg~ (C10) h y d r o p e r o x i d e s t h a t m a y have b e e n f o r m e d b y p r e v i o u s
e x p o s u r e o f t h e oil to air
Z - Vw2r~
gso (Cl 1 ) 3. Heating in t h e a b s e n c e o f air.
r o = effective radius N a t u r a l or a c t i v a t e d clays are m o s t generally used for
so = settling distance adsorption of carotenoid and chlorophyll pigments.
F r e u n d l i c h ' s t h e o r y a p p e a r s t o a p p l y to this p h y s i c a l sepa-
= Index-centrifuge size
ration. P i g m e n t s are a d s o r b e d in m u l t i l a y e r s o n clay parti-
cles t h a t have b e e n a c t i v a t e d n a t u r a l l y or artificially w i t h
W i t h a n y m o v i n g particle, t h e force (F) is e q u a l t o t h e mass
acid. F r e u n d l i c h ' s e q u a t i o n is
t i m e s a c c e l e r a t i o n , C1. i n a centrifuge, t h a t force is t h e
square of t h e a n g u l a r v e l o c i t y (w) t i m e s t h e radius,, C2. In
liquid m e d i a , force is e q u a l t o t h e d i f f e r e n c e b e t w e e n t h e X = Kcn
m
mass of t h e p a r t i c l e a n d t h e mass of a n e q u a l v o l u m e of t h e
liquid m e d i a (see C3). F o r s p h e r i c a l particle, t h e e q u a t i o n w h e r e X is t h e a m o u n t o f s u b s t a n c e a d s o r b e d , m is t h e
b e c o m e s C4. Here Ap is t h e d i f f e r e n c e in d e n s i t y a n d a m o u n t o f a d s o r b e n t , c is t h e a m o u n t o f residual material,
I I D 3 / 6 is t h e v o l u m e o f t h e spherical particle. a n d K a n d n are c o n s t a n t s i n h e r i t in t h e system. Acid ac-
T h e force t h a t o p p o s e s t h e r e m o v a l o f this particle or t i v a t e d clays are generally used for h a r d e r - t o - b l e a c h oils.
s e d i r d e n t a t i o n b y S t o k e s Law is e q u a t i o n C5, w h e r e n is A c t i v a t i o n is believed t o p r o c e e d b y r e p l a c i n g a l u m i n u m
viscosity o f liquid a n d v is t h e s p e e d o f t h e particle. If we ions in t h e clay s t r u c t u r e as s h o w n in F i g u r e 4. A dried clay

J. AM. OIL CHEMISTS' SOC., June 1976 (VOL. 53) 345