Use of Bleaching, Clays, in Processing Edible Oils

LOUIS L. RICHARDSON, Filtrol Corporation, 5959 W. Century Blvd., Los Angeles, CA 90045

ABSTRACT high. Therefore, the overall economics will favor the use of
Bleaching of fats and oils is a process whereby the acid treated clays over the natural clays for most com-
clay adsorbent is mixed intimately with the oil under mercial applications.
specified conditions to remove unwanted color bodies
and other contaminants. This paper describes the HOW BLEACHING CLAYS ARE USED
process and discusses the parameters and economics
Use of bleaching clays in processing of edible oils is
involved. simply that of mixing the clay and oil, applying suitable
agitation, elevating the temperature for the proper period of
INTRODUCTION time, and filtering to remove the spent clay.
The two types of commercial bleaching clays used in Mixing and Agitation
processing edible oils may be characterized as "Natural
Bleaching Earth" and "Activated BleachingEarth." Natural In order for a bleaching clay to perform satisfactorily, it
Bleaching Earth is usually a bentonite clay which exhibits must be mixed intimately with the oil and must remain in
adsorptive properties in its "natural state." The processing intimate contact during the bleaching or contacting cycle.
of this bentonite clay from mine to consumer is limited to In atmospheric type bleaching, the agitation must be
"physical" as opposed to "chemical" methods. Figure 1A is sufficient to keep the clay in suspension but not so strong
a simphfied flow diagram of such processing.
Activated bleaching earth is also produced from bento-
nite clay, but from a type which contains a high p r o p o r t i o n
A, NATURAB
LLEACHN
IGEARTH:BETONT
IECLAY
of montmorJllonite. The processing includes chemical treat- PROCESSNIG:
ment which se~'x~es to alter the clay and impart the high MNIN
I G HCRUSHING~ I GH~R~I~]
DRYN
bleaching activity. Figure 1B is a simplified flow diagram of
processing in production of activated bleaching earths.
B, ACID ACTIVATEDBLEACHING EARTH~ BENTONITE (MONTM(IRILLONITE)CLAY
It may be of interest to note that most bentonites ex-
hibiting high natural bleaching p o w e r are not suitable for PROCESS
N
IG:
activation, and most clays used for activated clay products
are poor in natural bleaching activity. Since it is essentially [MINING HCRUSHINGF-~TR;~;~ENTH WASHN
IG1
impossible to predict the bleaching potential of a new
source clay by analytical procedures, it becomes necessary
to apply the full processing in Figures 1A and 1B followed
by laboratory and commercial performance testing to
evaluate new clays~ In today's processing of edible fats and
oils, the use of acid treated clays far exceeds that of the
natural clays. This is due to the much higher bleaching FILTERING~ DRY
N
IG~ GR
N
IDN
IGH SZ
IN
IG
efficiency of activated clays, particularly when with very
dark oils and when the cholorphyll content of the oil is FIG. 1.Types of bleaching clays.

Oil Clay

Bleaching
Heat Vessel
Bleached
o Oil

Storage

Filtration 1
1
Spent
Clay

FIGo 2. Simplified bleaching process.

777
 778 JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 55

~
t
!L
,<,,

}
icottonseed
Soybean

Zl Soybean

r~

_J

u.

Optzmum Optimum
Bleach~,ng Bleaching
Temperature Temperature

t i l t
BLEACH I NG TEMPERATURE- I NCREAS i NG ---'--.=--
t I l I

FIG. 3. Effects of temperature on bleaching. BLEACH I NG TEMPERATURE- I NCREASI NG-----'-='-

F I G . 4~ E f f e c t o f b l e a c h i n g t e m p e r a t u r e o n F F A .
TABLE 1

Recommended Bleaching Temperatures a

Top decolorizing T i m e at t o p
t e m p e r a t u r e (o F) decolorizing
atmospheric vacuum temperature (min.)

Grease (inedible) 230 180 30

Lanolin 230 180 30
Lard 160 160 20
L a r d oil ( i n e d i b l e ) 220 180 20
Oleo stock 160 t60 20
Tallow (edible) 220 180 20
Tallow (inedible) 230 180 30
T a l l o w oil 230 180 30
Coconut 230 180 20
Corn 220. 18_0 2.0
i
Cottonseed 220 180 20
Linseed 190 170 20
Palm kernel 230 180 20 o~
Palm 3~ 325 20
Peanut 220 180 20
Rapeseed 220 180 20
Soybean ,, 2 2 0 ~1:80 20 .<,
Sunflower 220 180 20 --3
Tall 150-200 --- 30
Tung -- 180 20

aSpeed of agitation : : .............. 50-100 R.P.M,

Degree of agitation ................ S t r o n g b u ( i i 6 t violet
T e m p e r a t u r e o f oil w h e n
adding adsorbent ............... Atmospheric - 160 F
vacuum-temperature
o f oil w h e n t a n k is filled I I I
Vacuum ........................ 2~', (minimum)
BLEACHING TIME - INCREASING~

that air is mixed with the oil, thereby causing oxidation of F I G . 5. E f f e c t o f t i m e o n b l e a c h i n g .

the oil. In vacuum bleaching operations, the effects of oxi-
dation are negligible and agitation is usually more vigorous.
Note that temperatures for vacuum bleaching are lower
Temperatures than for atmospheric to reach optimum color removal. The
The optimum c o n t a c t i n g temperature is dependent upon effects of temperature on bleaching are shown in Figure 3.
the oil type and whether or not bleaching is done at This confirms a rule-of-thumb in bleaching, or adsorption,
atmospheric pressure or under vacuum. Table I shows that clay activity increases as temperature increases. As we
maximum temperatures recommended for various oils. can see, however, decolorization starts to decline after an
NOVEMBER, 1 9 7 8 RICHARDSON: USE OF BLEACHING, CLAYS, IN PROCESSING EDIBLE OILS 779

T A B L E II

Commercial Acid Activated Bleaching Clay

Property Typical value 220

Volatile matter, wt. %a 20

Free moisture, wt. %b 15
Acidity, mg KOH/GM (PHEN.) 1.7
Particle sizing, wt. % 200
Tyler standard screens
Thru 100 mesh 100
Thru 200 mesh 94
Thru 325 mesh 75
Oil retention, wt. % (laboratory) 35 180
Filter rate, CC/MIN (laboratory) 45
Activation index 100
Bleaching efficiency @ 3.0R 100
a L o s s a t 1 7 0 0 F.
b L o s s a t 1 0 5 C. 160

110
140

g
i00

120 I I I
2 4 6

90 CLAY ACIDITY MG, KOH/GM,

FIG. 7. Effect of clay activity upon FFA Increase.

i
>_ 80

u 150
ttl
70

140 T-200

60

130

50 I t ~ i I ==
50 50 40 30 20 10
VOLATILE MA'FI'ER - ~rr, % @ 1700~ 120 _ 93% T-200

FIGo 6. Effect of drying upon bleaching efficiency. ,=7,

i ii0
optimum temperature has been reached.
Temperature also affects certain other properties of the
= J 75Z T - 2 0 0
oil. One important such property is content of free fatty
I I I I I
acid (FFA). The relationship between bleaching tempera-
40 35 30 25 20
ture and F F A of the contacted oil is shown in Figure 4.
These relationships, then, dictate that temperature should PRESSP,A~, CC/H]N, (LABORATORYMETHOD)
be kept as low as possible to minimize F F A increase from
the bleaching operation, but high enough to yield the FIG. 8o Effect of particle size upon press rate.
desired color.
TYPICAL PROPERTIES OF ACTIVATED
Time at Top Temperature
Typical properties of a currently popular commercial
The time at top temperature of the bleaching operation activated bleaching clay are shown in Table II. These
is not nearly as critical as the actual temperature. Again a properties may be described as "physical properties" and
rule-of-thumb is that color removal increases as time in- "performance properties." The "chemical properties," i.e.,
creases. However, the breakpoint is usually substantially chemical composition, are not pertinent to use and per-
longer than the optimum time available, from a production formance.
standpoint, and does not come into play. The curves in
Figure 5 illustrate this effect at various temperatures. Most Volatile Matter
refiners have settled on 20 min as a practical maximum After washing and filtering, activated clays must be dried
time at top temperature. to facilitate handling and to maximize bleaching power. It
780 JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 55

~o TABLE III

140 Bleaching Economics

T - 2
99Z 0 ~ -200 Bleaching cost formula:
cost _ E(F+ G)+EJ H
130
1000 Lbs. Oil 200 10
5 B = Oil retention of press cake -- wt.% dry basis
i
D = Moisture of adsorbent as charged -- wt.%
E = Dosage of adsorbent - wt.%
,,=, F = Price of adsorbent -- $/LB delivered
120 93Z T-2OO
u G = Handling cost of adsorbent -- $/LB
H = Price of decolorized oil - $/LB
uJ ja = Oil retention of press cake - wt.% of clay as charged

110 aOil retention = B (100-D)

100-B "

Clay Acidity
100 1 I I l I
If the activated clay is washed c o m p l e t e l y free of resi-
25 30 35 40 45
dual acid, the bleaching p o w e r is drastically reduced. If the
Z OIL RETENTION (LABORATORYI"ETHOD) acid value of the clay is left at a high level, the increase in
F F A of the finished oil will be unacceptable. Therefore, a
FIG. 9. Effect of particle size upon % oil retention. c o m p r o m i s e m u s t be reached for the clay in question.
Figure 7 illustrates the relationship b e t w e e n F F A increase
and clay acidity.
140
Particle Sizing
The particle size of the finished clay is relatively easy to
c o n t r o l by air separation following the grinding step. It has
I 130
b e e n d e t e r m i n e d that grinding to e x t r e m e fineness will
increase the bleaching p o w e r markedly. However, the
factors of filter rate and oil r e t e n t i o n will be adversely
120 affected. Again, c o m p r o m i s e is necessary. The particle size
data seen in Table II represent that compromise. T h e
7 effect of particle sizing on filter rate is shown in Figure 8
and on oil r e t e n t i o n in Figure 9.
11o
i.I
Activation Index
The activation i n d e x o f a clay is an arbitrary value
100 assigned to a specific p r o d u c t of the clay activation process
and corresponds to the bleaching efficiency c o m p a r e d to a
standard clay. Details concerning this p r o p e r t y are
90 I i i i i p r o p r i e t a r y to the clay p r o d u c e r and vary greatly a m o n g
40 50 60 70 80 90 different clays. E x a m p l e s o f the e x t r e m e l y great variations
found b e t w e e n source clays for activation can be seen in
"IREATING SEVERITY
Figure 10. All of the clays p i c t u r e d here have been used
FIG. 10. Raw clay selection. c o m m e r c i a l l y for the p r o d u c t i o n o f activated clays.
U n f o r t u n a t e l y , the b e t t e r clays such as " C l a y C " have been
long since depleted. Thus, the use of the m o r e difficult
has b e e n d e t e r m i n e d that m a x i m u m bleaching p o w e r of the clays has b e c o m e necessary and is an i m p o r t a n t factor in
clay represented in Table II lies b e t w e e n 18 and 22 wt % clay costs.
volatile m a t t e r ( d e t e r m i n e d at 1700 F). Figure 6 is a
graphic illustration of this effect. In regard to " f r e e "
m o i s t u r e c o n t e n t (loss at 105 C.), this p r o p e r t y is n o t ECONOMICS
usually controllable e x c e p t as it follows as a f u n c t i o n of U n f o r t u n a t e l y , the e c o n o m i c s o f bleaching clay use is
total volatile m a t t e r . In a d d i t i o n to drying the clay to a o f t e n based u p o n t h e cost o f clay w i t h o u t considering over-
specific volatile m a t t e r level, the m e t h o d o f drying is signi- all costs. In this regard, I would like to present a simple
ficant. It has b e e n d e t e r m i n e d that speed o f drying affects m a t h e m a t i c a l f o r m u l a which m a y be used to c o m p a r e use
bleaching p o w e r . T h e r e f o r e , flash drying (high speed) e c o n o m i c s of d i f f e r e n t clays - Table III. This formula is
e q u i p m e n t is widely utilized to take advantage of this valid for use with l a b o r a t o r y data as well as data from plant
phenomenon. tests.