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Degumming, Refining, Bleaching, and

Deodorization Theory
JOHN C. COWAN, Adjunct Professor of Chemistry,
Bradley University, Peoria. Illinois, USA

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

344 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

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