Bleaching TheorY and Practice
-
T.K. ll{ag
Resrrarch Cent.er, (lanadil Packers Ini'., Toronto. C"ntario M6N 1K1' Canada
Introduction
In recent years, the process of bleaching hls.inre-a
ieived considerable attention. This has resulted
mr-rch better appreciation of [he fact that the process
affects oils beyond the removal of colored material
and that, in addition. it itifluences the stabilityof ed-
il,te oit products to a decisive extent. Research and
[Vater DegummiBg
develophent efforts have led to improved adsor-
bents, especially improved bleaching qlays, and the
development of sllthetic materials. There is also a
better undersianding of ttre effect of process condi-
tions and tiris is, to some extent, being reflected in the
process arrangements being used. . .
As these brfuf remarks indicate, bleaching is now
recognized as one of the most important "refining"
tr"pj ir', edible oil processing. It is applied at various
.tug". in refinery operations-deperrding on prefer-
enc"e. Figure I sl.tows that in the refinery process se-
qrence,bil is bleached after alkali-rehning, or, in pro-
iessing'of lorv-phosphatide oils, bleaching is the main
"cleanlup" stage. Optionally, oils may be bleached
again aiter hldrogenation to assist with nickel
removal.
Theoretical Aspects of Adsorption
Bleaching
Bleaching of oils is achieved by a process of adsorp-
tion. Polir materials, rvhich are dissolved or sus-
pended in the oil in relatively low concentration' ar€
idsorbed on the surfaces of solid particles of an ad-
sorbent material. These surfaces have electrically-
charged sites due to inhomogeneities.in the crystal
latticls, which make up the particles. This is shown in
Figure 2 (1) on the examplg 9t-the basic structure of
blSachinj ilay and Figure 3 (l), especially, showing
the activ"e sites after altivation with acid.
The foregoing considerations show that adsorption
of comporindJis governed in a major-way by the
numbei of adsorpiive sites available and,qtso,'by-the
concentration of polar material in the oil. Depending
on the nature ofihe compounds to be adsorbed and
the nature of the adsorbent, there may be different
ciegrees of adsorption from physical adsorqtion, in
w'hich Van der Waal's forces between molecules hold
t he adsorbed species, tc chemisorption or even chem-
icai reacr.ion ivhere chemical bond formation of a
fi1()ie or iess stable naiure is involve<l. A-n equiiibrium
lir:t*'een 6i1s afl-s{)rbed and the dissriived. t;r sus-
pended. species is esta,Sir*.iied '.2''t.
l'he main i'acir,rs '.;l irr,p'oriamce in iiescribing aC-
sitt'pticn bieaching al'e e:ipressed in an er.',pirrcai re-
iaiir;ir kr,o* r, a-s tir.e FreunCiicl equaiic,'rr. It applies to
ru.risorpiion c-rf a sclute i-r':im <iilute -"oluiir-;n on a soiid
-.urfiiL--e i2). as is the t:r^se in ecible i:il i;ieachir'.g:
Crrde C)il
rt Extnction Plant
( !
I
I
i
Alkali-refining + Sqp$o{*
I
Prci{8
I
i Add Prelrsl
Bleaching
-Bleaching
Hydrogemtioo
(
I
Bleching )
Deodorizing
Deodorizing
( Physisl Refining )
Fig. l. Main steps in edible oi-l processing.
C* = k {V(C" - C*)}n where C* = the equilibrium mass
of soluielvdlume of solution, V = volume of solution/
mass of absorbent, C6 = the initial mass of solute/
volume of solution and k and n are constants which
depend on factors other than the concentration of
soiute and adsorbent, namely, temperature and the
nature ofthe adsorbent and ofthe solvent.
The above equation is one form of the Freundlich
isotherm. The ielation indicates that adsorption at
fixed temperature and adsorbent pro-perties de-
pends on the concentration of the solute, for example
ihlorophll and the concentration of the adsorbent,
usually acid-activated bleaching clay. Graphs of the
equilibrium concentration of various compounds to
be adsorbed versus the amount ofadsorbent used are
often prepared in investigating the efficiency-of dif-
ferent adiorbents at the same treatment conditions,
especially at the same [emperature. Lovibond red, or
chlorophytl concentratior in milligramsi kg' for ex-
ample, oi tight atrsorbance at the apprcpriate wave-
length can be used to express concefitratlon'
The Cornpounds to be Adsorbed
As alreadS'' indicated, bleachirg encompa-sses much
more than removing cciored compouncis fror, oils'
Tabie i iisrs the matirials which are of interest.
As pointed out earlier, adsorpiion. depends espe-
ciatl;vbn there Lreirq sorne eiectrostatic imbaiance r;n
li)?
 108 T.K. Mog

t-olrrcxttotlAL i€?acrctlTArrcX t-o llac{ ttot{At iE?R€ !E rarATtOtl

aor . tt'
f.lr.htdral 4!lt rld
t.t.t-
- {O'-lo{frte-
Ool.iadnl
frrrr i6Pl g3r.;1 1o
l30r-t0lfrf0'
-
ftl.rd3
lO' rtf
t.larltraa Callr. 6*.1
(rrrrlly lyarrtodl- L.r.t ClrF-t
l:l.rl.t.r Clrl..l
ll.l Clrr. o

lYPlclt cfiEaflcAr rof,strL^:

Ocrrgaia aalrrl.r..r.Ortaa.a .aal{..
Qlycrcrylr a alllaa.. .3oaalcialtt tlrrlerr r l.( r rar,ul-1 oro( o{rr.
( I .1, r l. ar.1,

Fig 2. Structure of montmorillonite i I ). (Sodium iorm).

I. ACIO ATTACKS OCTAHEOf,AL LAYER 3. STBI,,CTUAE OISRUPTED-

sURFACE AAEA II{CREAS€S
o -r,F
Wcno
a+o
|(a
reb o
9<
icr
{Q* O
a CATtOilS RELEASEO FROU 8TRUCTURE
EXCHIt{oEo FoR CALC|UI| cATtoNS
^gLO
4. ACto AcTtvAT€O CLAY WttH AC|D
c^Ttoxs tN EXCHAxGE 8|TES

Fig. 3. Clay activation by acid attack (l).

the part of the adsorbent as well as the compounds to

be adsorbed. It is evident that the properties of the TABLE T
compounds listed in Table I cover a wide spectrum in Coinpounds Adsorbed in Bleaching
their degree of polarity. Further, there is considerable
variation in molecular size, which affects access to Colored compounds
the interstitial surfaces of adsorbents. This is shown Carotenoids
in Figure 4 (1). For these reasons, it is not surprising Chiorophgioids
that there are differences in the ease llith'\vhicii
some of these cor'.pounds are adsorbed. and that Others
some adsorbents may be more effective. oi not effec_ Primar-r.' oxidarion producis breaktio*.n )
tive at all, lr'lth some of these compounds. 1
Siecondar r- oxida.ticn products
Iron, nickei
Adsorlrents Llsed in Bleaching Soaps
As a!re.ad-l-indicaieC, acid-activated clal,s are usetl in Phosphaticik r:ompou nci.s
Dieacnlng. i'he], are b1..far the r,najor acisorbent mate- Polp.arcmattcs
 Bleaching ThanrY and Prartice 109
-
t. PIGMENT APPROACHES ACID CATIOH ANO 18
on clay structure and activation. Coupled rvith sur-
PROTONATEO face aiea are particle size and pore size, lvhich affect
filterability and also oil retention.
Additional factors, somewhat complicating the ef-
?4 fecr of clay manufacturing practices on clay proper-
ties, are the amount of free acidity and free moisture
left in the clay after activation. This will be discussed
further in connection with the adsorption of various
compounds and in connection w'ith side reactions.
As indicated before, in addition to actir-ated clays,
especially active-carbon alid, more recently-, synthet-
>* ic silica oxides are in use.
Active carbons have been used in edible oii bleach-
ing for a longtime. Their use has not been extensive
2. ACiA CATION/CARBOTGUM ION COMPLEX FORMS ANO mainlybecause of cost, high oil retentidn and di{ficult
HELD BY ELECTFOSTATIC ATTRACTION handling as a powder. One important use is in the
adsorption of polyaromatic hydrocarbcns from some
.p oils, especially fish oils and some coconut oils (3).
These compounds are not effrciently ad*sorbed by
.'l--.)ia clays and cannot be removed economicafu by other
c$,\,L means.
Other uses cited in the literature (4) are in soap
removal, in green pigment removai and in milC
bleaching of larri. There is no el'idence that active
carbon is used to an-y significant extent in current
refinery practice to adsorb chlorophl'lloid com-
<C pounds from canola or soytrean oil
In recent years, research into synthetic silicas ha-s
Fig. 4. Pignrent adsorption by activated clay (1). resulted in compounds whieh have utility in adsorb-
ing secondary oxidation products (aldehyde_q, ke-
tones), phosphatidic compounds, and soap (5). No
rial used in the industry. Particle sizes range tpically significant direct adsorption of carotenoid or chloro-
from 20 to 80 microns. Other adsorbents also of some phylloid compounds is observed with some of these
rmportatrce are activat,ed carbon, eilher in porvder or silicas, but the adsorption ofthese by subsequent clay
granular ftirm, and more recently, s;Trthetic silicas' bleaching is claimed to be more efficient (5). The basis
ir.lth particle sizes averaging about 20 microns and a for this observation is the greater affinit-v- of some of
narrorver particle size tlistribution than indicated the oil contaminants for different adsorbenls, in this
above for activated cla1s. Because of the importance case the silica oxide. Recently, a sSmthetic silica was
of the bleaching process in the refining of edible oils described in the literature (6) which is claimed to be
arrci the import-ance of activated clays in bleaching, suitable for the direct adsorption of chlorophylloid
there iras been considerable development in recent and carotenoid substances. Evidently, as already in-
improve the effectiveness of clays.
-)'ears toproperties dicated, there is considerable research effort in this
Clay important to bleaching and which area. One impetus appears to be that rn'ith some of
can be modified in the processing of clays are listed in these materials regeneration for reuse may be
'fable 2.
possible.
The effect of surface area and degree of activation
on adsorptive capacity is obvious from the discussion
Adsorption Isotherms
TABLE 2 Because of the variety of compounds which are to be
Important Bleaching Clay Properties removed from oil by adsorption, it is appropriate to
review their adsorption isotherms. This gives an in-
-{dsorption sight into horv efficiently adsorbents, especially acti-
Surface area
vated clays, are able to remove these compounds.
These data are due to Delaney and Ungermann (1).
.A.ctive sites on surface
Figure 5, gives data on red color removal from soy-
i),,t't :ue bean and car'.ola oii using a varieq'- of acid-activated
-ii s (,i ,
clays. For soybean oil, about 0.5% of the trest clay used
1..i-l:..,
,li ttllt \ in these tests and for canoia oii about 1.5% rvere re-
]l,r i.sr Lr re .jLlirt cni quired to achieve a color of 5-6 lolibcnd red. Figure 6
'i iii
deals r+'iih chlorophyii rernot al from the salrre oils. To
c raf : iiitl' ach.ieve a residuai concentrar;ian of 5c micrograms,l
!':r r i 1 r' it' s izt: i ai'ibc s u ri'ace area .i
kg wi-th the besr ciay, so1.&ean oii w'ith 0.? milligramsi
".-.
i i:i :-(.1!,trii(,ll kg of chlorophyll regulreci a}out 0.5i'i' cia.r- and canola
oil. starting w-ith a much irigher concentrarion of 2 i.7
I)at-t ii !t, size
m.illigramsi kg. requlred about i.E;. These are fairl.v,
 lt0 T.K. Mag

from canola oil. Obviously, iron should be removed in

'&+tle alkali-refining, or, when bleaching low-phosphatide
(tr tr*rr) oils which are not alkali-refined, its removaf should
be assisted by an acid pretreatment prior to bleach-
r-e., tao ing clay addition.
t .--otol
a---Y.e. ?tr.
Figure 8 deals with phospholipid removal^ Again, to
achieve the desired removal of phosphorus to a max-
I CrrerooOt..*r.) imum residual concentration of 2 milligrams,lkg from
l7 requires a much higher clay dosage than would

t
E' probably !e required for red color and chlorophyll
removal. This indicates that for phospholipids, as fbr
Er
b metal removal, process steps other than bleaching
g. \ should be considered alkali-refining, or acid pre-
treatment,pr utilizing -an adsorbent much more effi-
3 \ --\- cient in the removal of these. \
\ The effect of this latter approach is shour in a
a \-r- \ siudy ciue to Pryor et al. (5). Figure g shows the rela-
tivel_v better efficiency of a synthetic silica in phos-
pholipid removai com.pared to an acid-acrivared
2A tI,
Ctry Dorlgc (fl
Wrtr tlcgm.d
Fig.5. Bieached oil lc'ribond red isotherrns fcr scl,bean and
canoia oii (l). .I a r- o'l€o
l,
._ _ o, io6

C.-a.et?a0r-)
^ a.a

ll t a tao
5."
I
I
aa
. toa \'
-Ee,
-*
a---ttr !l
trr
a.'
oq
e a.t
r a a
E
c, a
o
o 0 1 lo ll
a.tti.i ' cray Do'qg. ttl '
.9 (, ta rea)
c
()
.n \'.
_ \ \. _*r".
Fig. 7.
(1).
Bleached oil iron adsorption isotherms for soltrean oil

1\\
D
23 !l, It
ta
Clry Dolre.(t)
l,
la r -- &'tCO
Fig. 6.
Bleached oil chlorophyll adsorption isotherms for ll a\ o__e,!o6
soybean and canola oil (1). ta
\
It
?,,
tl,pical clay dosages used in bleaching these two oils.
grt
rc
\
!l
Chlorophylloid compounds must be removed to the !r
qa
\
above mentioned lorv concentration of 50 micro- Ot
E'
grams. kg or lolver to avoid rapid oxidation of rhe oil Aa-
in rhe presence of lighr (7). a \ '!-
a
Figure 7 deals.,vith iron adsorption. Iron is the ma- I
jor pro-oxidant metal to be removed froni oils in the a
course of refinery processing. It can be seen that il I
a
irc;n is reiatively high., about 0.8 miiiigran.s,'kg. clay ta .'! u
riosages in ihe order of lJi. are required to io.*'ei it to Crrr Dor{. {t}
tl..e Cesired le','el of belou' 0.i ri-,iiiigramsik{. ?his is
n-.uch in e\cess of the cia1.' ciosage needed rii achier,u Fig. 8. l-iitacl'r+rd orl h r;splr r-, ii pi <i aa1 sll-pt i()n rsc t h i, I.'rs tr i r
adequare red ccior and chlorophl,ll removal. evep.
1-.

il;i i.i ).
_sc.r'i*,.ari
 Bltruthirtg * Thetrg atd Practk:e lll

Next in the discussion is the effect of bleaching on

hleact'.ing earth (AtsE), and F-igure-10 short's the in-
,:i"i.*a Smciency of subsequent chlorophyll adsorp oxidation products. It is well-known from experience
;i;. l* activaleri cla.r'. It should be noted that t his that hydr6peroxides present in the oil, or formed
,,,r.ticutr. s;rlthetit' silica does not adsorb chloro- duringbleaching, are decomposed during bleaching.
i-i.,.ii"ia or iarotenoid compounds to any significant Primarily aldehydes and keLones are formed on de-
u'ith a,qhos-
!ii"n,. Canola oil was used in this studyand composition. A measure of the concentration of these
content of 18.5 milligramsz/kg a chloro- secondary oxidation producG is commonly obtained
"}.r,,i"tc,,ntent of 22.8 milligrams, kg' Lrv the anisidine value (8) of an oil. Aldehydes and
i,irvii kltones, because oftheir polar structure, are adsorb-
able on active sites of adsorbents such as clay-
r5 Figure 11 shows the isotherm of the breakdolvn of
hydfuperoxides and the adsorption of the break-
dbw'n-products (1). It is evident that activated
bleaching clay catalyzes the decomposition of hy-
t2 droperoiides'and that clay dosageq of 1-2% are
TriSyI neehed to achieve this decomposition with- oils of
high peroxide vaiues of 5- l0 milliequivalentsz'kg Ad-
soipil,rn of the secondary products is-rel?tivel-lz inef-
9 fici6nt. To achieve an anlsidine value of 2-3 maximum
Phcpholipld requires clay dosages of 2-3%, whicl-r is-quite co:t-l]'-
gnisiOine values below 2-3 afier deodorization of the
trosding
w% oi-i. r+'hich removes very roughly about 50iir, are re-
6 quirements
- for good oii stabiiity (9). -
This corrrparison of adsorption isotherms pror''ides
a good appreciation of the behavior of the cor'-
poinds of interest in bleachir-.g. Ii aiso points out the
need for effective alkali-refining, or acici pretreat-
ment, and the need to protect oils from oxidation. If
ABE any of these are neglected, it is evident that bleaching
can become quite uneconomical, or poor qualit;" oil
products result.
o246El0 T\vo additional edible oil constituents of interest in
adsorption bleaching are free fatty acids and toco-
Ptosphorus, pPm pherols. Free fatty acids are adsorbed as w'ell as
iormed. This affe-cts bleaching efftciency and oi'l
Fig. 9. I'hospholipid isotherm comparison for a slnthetic losses. Usually, free fatty acid concentrations remain
silica and an activated clay (5). unchanged, oi show a small net increase in bleaching
at abouil0O'C with acid-activated clays. Thble 3 gives
some data on the effect of clay dosage, oil,/clay con-
70
tact time and contact temperature on free fatty acid
formation. It appears that differences in clay dosage
0.6% TriSyl and contact time have little or no effect, but bleaching
60 temperature signilicantly raises the free fatty acid
con6entration during bleaching. From the above, it
0.3% TriSyl
hereat

TABLE 3
Chlorophyll Hydrolysis in Bleaching of Soybean Oil (0.14% FFA)'
L,oeding
w%xl0 30
No Pretrcat Bleaching
Bleached
Ciay
dosage Temp. Time oil
.C min I-FA ''
20
1.5 r25 3 0.30
.l 0.47
r0
,-) 125 3
i.e 170 3 rl.6'l
.-f rl I ?t! .) (i.6r;
t.5 125 30 0.25
rJ 5r0t5:0 2{i t:;) ;-ii_l
'.).:7
Ctl croph-t'll Conc- PPm l.a) I /t, ,,I,I ( t l).1
') il r :il 3r) (l. ir'-l
Pig. 1ii. Eil!'t'ri si a sl.'nthelic silica prerrealment +rr cilr'ro
l:iri ii is,rtherrns irr :r<:ti:;att'tl t'la-r' hiearhing (i ;. "l-rrpublished daia - T.X. .Hal
 112 T.K. Mag

to

t
a
.E 7
!

IE) I
-t
c t
o
a {
!x
o !
a
A
,'
\
t"
G.

Ctay Oorrgc (*l

Fig. f l. Bleached solfoean oil oxidation value isotherms (1).

t,
l.lt
Cr t6o
t.t o-- Gr106
E
q. trr
o
5i
-: t.
6,!
og
o
o crc
F

GT

e.s

ct
CIay Dosegrc {s}
Fig. 12. Tticof:her,-rl :e i.rlearheri, deoiiori;l.ed sur..bean oil.
effect of differeni cia'; dr-isages ( i ).
 Bleaching
-
rrlay also be inferred that differences in free acidity
an.i *olst.,re content of clays have only a minor ef-
fect on free fatty acid formation during bleaching'
- Brimberg's data expressed in tl're form of a loga-
tocopherol cbncentrations are usually lowered
somewhat, apparently depending on clay dosage and
oiso .tay einiiency. Figure 12 indicates that for a 1%
.ir:'"tug" a lowering of about 10% in total tocopl-tqlgl
coricentiation occuis in bleaching of soytrean oil ( 1)'
Kinetics of Adsorption
The rate at which the various comlrcunds of interest
in bleaching are adsorbed is, of course, an important
asnect of tlie process. It especiall-v affects considera-
tions of proceis design and the question ofsuppress-
ins un\a'inted side reactions. Little investigatil-e work
"available, but in recent years the subiect has re-
is
ceived more attention in studies by LI. Brimberg (10,
I I ) and also by IvI. NaC\'( 12). for example. These srud-
Lr'ru"t" concerned especiall5'with the adsorption of
-hlorophylloid
and caiotenoid compou-nds. Figure 13
summirizes the findings by Brimberg It can be seen
that at a bleaching temperature of SffC and usir,g 1%
of an acid-activated clay, adsorption of chloropLryll
and carotenoids from rapeseed oil approached equi-
librium closely within 5 min of contact time- There
was a slight improvement in the amount of material
adsorbed-up to20 min. Additional contact beyond 20
min. did nol result in signi-ficant further adsorption-
/t\t
Fig. f 3. Adsorption of carotene and chi,:rcphyll n'ith iime
: . i, ,n5i! Fl-'. E0"(- I r I i) r.
ThaW and Practirc 113
These data imply, also, that at the usual bleaching
temperatures, 95-110'C, maximum adsorption is
achieved in less than 20 min of contact time.
rithmic equatio4_produces the following function:
logC",'Co=-kVt
The constant-k increases with the amount of clay
used and the temperature of bleaching. With some
oils k also increases with increasing amounts of water
present in the oil/clay system at t = 0 (11). The same
author also found that agitation beyond that re-
quired to keep the adsorbent (clay) in uniform sus-
pension in the oil, or slurrying instead of adding clay
as dry powdq, did not accelerate adsorption.
No data on the kinetics of adsorption of oxidation
products. metals and phosphatides appear to have
been published. Some data are available on the effect
of moisture on the removal of trace mteals (i3) and
phosphatides ( 14). These data imply that the rate of
adsorption of all of these compounds is simiiar to
that determined for caroiene and chloroph3;ll.
As indicated earlier, the tirne required for rnaxi-
mum adsorption is also important in connection witl'.
side reactions taking piace during bleaching. Side
reactions of interest are:
Heai-cieavage (breakdorvn) of caro'-enoicis
Hydroly'sis
Oxidation
Isomerization (including conjugation)
Polymerization
Heat-cleavage of carotenoids (heat-bleaching) at
usual bleaching temperature and time (100'C and
15-30 min including filtration) is taking place to
some extent as documented, especially with palm oil
(15). Its importance is primarily in the fact that it
makes it difficult to judge bleaching results by con-
trolling red color. It is estimated that from 5-20%
reduction in red color due to carotene breakdown
occurs with soybean, canola and palm oil during
bleaching. This breakdown would also occur in subse-
quent deodorizing.
Hydrolysis was discussed earlier.
Oxidation, isomerization and polymerization are
all reactions detrimental to oil quality. They are to
some extent catalyzed by bleaching clay and take
place at bleachingtemperatures and rates which can
produce significant changes in minutes. Oxidation is
suppressed by operating under partial vacuum.
-and
Isomerization polymerization are minimized by
limiting bleaching temperatures and time (16, 17).
Bleaching Processes
There are many versions of bleaching processes in
use. In most modern plants these installations are
intended either for serni-continuous or continuous
operation. Ferv modern plants op€rate batch pro-
cesses. From the di-ccussicn on bleaching fundamen-
tals, it fcilows that batch processes can hai e sericus
drarvbacks. especiali-v ir-r respect to the time required
to heat the oii anC in resp€ct to the oili'cla1'contact
time. Eoth of these tend to he excessive and hence
allow' unwanied sicie reaciions to take place to a
greater e:{tep.t.
 I l1
Fig. 14. Conrinuous bleaching s$item (DE SIIET) (18).
An example of a modern process for continuous
bleaching is shown in Figure 14. It senes primarily to
describe in detail modern bleaching praitice and to
point out desirable a^spects as deveiop-ed in the earlier
discussions.
Oil to be bleached is heated to bleaching tempera_
ture, usualll- 95-110"C, the adsorbent is ;dded and
rvetted by the oil for dispersal, and the mixture is
cleaerated, and has moisture removed. Usual adsor-
bent levels are from 0.2b%-B% of acid-activated
bleaching cla1,, or 0.192, to O.bit carbon or silica. T\t,o
porvder feedingsystems (not shown) which use more
than one adsorbent, or a filter aid iogether w"ith an
adsorbent are often used. Filter aid uiage ma1.be as
filter precoat only, or at rhe rate of abou"r 1091,;lcla.v
usage.
,u" acid, or."dry," pretreatment is to be gir.en prior
I,f
tt.r bleaching clay addition, the acid is mereredinto
the heated oil stream a-nd uniformll,dispersed by an
in-line mixing device. Then contact tirne^is allolved in
a stirred reactor vessel as shorvn in Figure 14. Acid
nri-xing methods are available (19, l0)'-r.fricir are ca_
pable olgenerating a large inter:facial surface area fr.rr
:tcid oii coniact. Tilis itlit.-iates the use r_;f a stirred
reactor, -q:r., t,s ar:id anci faciiif aies stock cliirn{e-s.
Ale'rage residencr. ti;rie in tlie ntain i;ieiichi-ng se,i:-
ti<ili ofthe i)rocess, rviiicii is *iiLtipoeri *ith arr igiru-
t,.:r'il this e x:lniJ,;ic, i-s frr;nt ab<rui:i-.Jii r..tin. Titi,j'res_
irience tirrie st,-,iirii., tnat-i;e uli,ier \-ar..,,lilfil of ;1i'i-151.t
t()i't' u'iri. rt()r-ttiiiiial iii-r.ing,.<it- ii m:ir. l-re it: i$.| .\iase:
ir itl-r ilt+-' si,i,oitrl s1.:,rqi' unrier pr.r,ra.ur.e itr sorne pro
('.-'s,i{'s.(.j;1,?1;. a-litr'ri. sir'iint lJ irrie, ti,ri i'i,1 ..u,1 .r,.11
Il ltiriirj li-ir'ai-iaI..i(.iii ii_gii:tir;l-:,. -llie ii.,,.risti:i.r-.,(lli(liti
T.K. Maq
tall! ?aflA
,:^-!.h" oil clay mixture after drying should be about
0.. lor according .to several authorJ(13. 2l). Excep_
tions are also cited in the literarure (ll. i8,21) in
respect to adsorption of phosphatides. metals ind
chlorophvll, as ment,ioned-befoie. The effect of niois-
ture on.adsorption is probably quite complex. Its ma-
nipulation may in some cixes produce significant
bleaching economies.
Filters. are_usualiy of the tank r1pe, liorizontal or
vertical. b,ut filter presses are also ifitt'usea. Keeping
the adsorbent in uniform suspension in tank filters ii
important and is said to be mbre easily accomplished
in a r-ertical filter tank than in a horizontal filter tank.
Average residence time in tank filters is approxi-
mately.l 5 min and just a few minutes in lilter presses.
Depending on the size of the main bleaciring section
and the tlpe of filter used, average total oil,,6lay con_
tact time can be more than 10-20 min, u,hich appeu.s
to be the best compromise betu-een marimum ad_
sorption anci suppression of side reactions.
A significant portion of the total adsorprion taking
.
place in bieaching occurs in filtration. The oil passinfi
thrrrlgl 114 filter cake, which is continualll coilecrinfi
on the filter medium. is in corrtact rvith i r-eq_, higfi
('()Il{:rriiltt-alion r-rf 3d51-r1bent. This acsorbent Stlli h'a.s
-.onte frt,e iittir,e site.s. rr'hic'h represeilt significant ca_
paCII.\' ii,r- iur-ther adsorpl i,rit rr!- pi;lii; i.r:i-1-1pt;unii._*
I)i tseitt ii: 'Ie oii pirssi.ng ti-,rrr.rigir iii+ fijrr.,r ..ait Ti;is
arlso.r'p t t, :. is oi t lt e -1,.er.i'li lil in g bi.,i- i3pe a i.: ii i: r,., : r.i
t
Irlr>nl',' k:r,,ir'ri a:i ihij *il!-i:ss trir:aih i,iie.,i." Initia.ilr.
ii{ i Liti'r'r.ilt1'..ri Ilr.','t,t': iii'ltris*i-iii.lll :iit, silirr:li ,:.rh:ril.r-
lri. t,r:i ii, ,\:.. iii lulrrrri:rl;;rI.it!-,;,-i,eiii ll;-,.i,.i*- a,i,-ii
tlcitiil :ir'l - :1riir r, {. iii}itr.ii'r: ilrI.i;:r{i-riir.:! ilit i.!tra:ii-;n
 tsl.e<u:hing ThatrY and Prat:tk'e 115
-

cvcle.'I'his adsorption occurs under pressure'
'
Tire desired bleaching process capabilities can now
be sunrmarized as follows:
a) Maximum efficienc-v in removing undesirable
compounds, that is,
i). enough mixing to keep the adsorbent uni-
formly'susPended in the oil
ii) optimum temperature for adsorption -
iii) oltimum moisture content of the oili adsor-
bent slurr;'
iv) sufficient time for adsorption to take place
b) Suppression of undesirable reactions. that is.
i) limit temPerature
ii) limit air access
iii) limit time.
1b these points the following ma:{ be adCed:
clay'- addi-
c) In acid pretreating p-r-ior to b-leaching
possible
tion, ensrrre thai ihe smallesi
droplet size is achieved for best acid,roi! contact'
Thii facilitates phosph'aiide and metal remot'al.
and also facilitates excess acid removal b1'' ti"e
clay.
d) Achieve ail oi the above w'ith rninimum resi-
dence time in the equipment to facilitate stock
changes.
Process and Quality Control of Bleaching
Efficient bleaching requires that the key aspects of
the process be monitored and controlled. These as-
pects are listed in Table 4.
Tire frequency with which measurements are re-
quired.,,arles. In process control, all items listed are
,',-,n." o. Iess continuously monitored and adjusted, if
required, except for moisture in the oil;/clay mixture'
Molsture detefmination serves to ensure that the op-
timum moisture level is achieved for a particular
bleaching task.
In quaiity control, red color and, -with some oils,
chlorophyli are routinely monitored. In addition, the
TABLE 4
Process and QualiW Control of Bleaching
Process control
Temperature
Pressure
Ailsorbent usage
Filter aid usage
N{oisture in oil,'claY mixture
Ciarit-v of f rltrate
peroxide value and free fatty acid content are
checked, but less frequently. The anisidilte l'aiue, iron
concentration and conjugation values may be moni-
tored in special cases, especially in connection rvith
problem oils.
Disposal of Spent Adsorbents
Increasingly, requirements are that disposal of spent
adsortrenis-be free of negative effects on the environ-
ment. This means, primarily, that the oil retained in
adsorbents must be reduced to low levels. This is done
by various methods using organic soll'ents, hot waier,
oi a combination of these. Combustion is also used. A
comprehensive oven'iew of disposd- methods \l'as
presbnted by Fahn and Zschau (22). No regeneration
and re-use of activated clay seem possible at present,
but more effort may well be expended in the future to
investigate '.his further. Also, recent work on syr'.-
acid
theric lilica arisorbents (7) suggesls that re-use of
this t1'pe of adsorbent is feasible. Granular active car-
bon is routinei-v regenerated and re-used in other
industries.
Summary
Bieaching has assumed increasing import,ance rela-
tive to other refinery processes. It is essentiaily a
process of adsorption of dissolved and suspended
iompounds from triglyceride oils onto solid surfaces
of ari adsorbent. The compounds to be adsorbed are
present in very low concentrations in the order of
milligrams/kg. The Freundlich adsorption isotherm
desciibes the process best except for the press bleach
effect. Acid-activated clays are mostly used, but syn-
thetic silicas and active carbon are also applied.
There is considerable activity in adsorbent improve-
ments. Investigations of the kinetics of bleaching
show that the process reaches equilibrium in min-
utes. Side reacfions are especially important to oil
quality and oil losses, making it important to limit
adsorbent/oil contact time and temperature. Many
process versions exist reflecting past beliefs and
more up-to-date knowledge. Modern processes oper-
ate in the continuous mode with good control of con-
tact time and temperature. Equipment for acid
pretreating is usuaUy also incorporated. Environ-
mentally sound dispoial of spent adsorbents by using
them in bui-lding materials or removing the oil before
dumping in landhll is now much more a requirement
than in the past. Re-use of activated clays does not
seem feasible, Uut re-use of the more expensive silica
and carbon adsorbents is being investigated'

Qualit;.'control References
Reri color l. Delaner'. K A.. C.B. Ungertnant-,. Ettiv-tirv' Ari's<.rt';lrit'i'
('li lori;ii h1'l l nical Presenl ai ion ;iiil H:ir-\ l-r a\\'
B I eo,:h i ti g /1. l-t'r:h
'leroxide valtte Filrcli):rrtiiership.,3(r 1 00 L'hagrir Iilr ti.. ('ii'*. ci:rt:ii.
.r'nisi<line valLre )i,io 4* i i-i. L'.S.A.
(
F rr:,.: fait),' aticis 2. lreSirlii. Fi.l-.. in -lfir's-s Irtl;'i.sii't r t'v't'iitiiit;'':' :ii'rl r'<itl '
Irr-n (nickel i "^A.tlsor;:,iiltl anri Ilil, Iirr'|ialt{t'" ir'i' 'rti '-rsj
L'on.!ugation \It'ilr=ri iliii irrt. Iio,ik ('o.. liiri
116
T.K. Llag

3. Sagredos, A.N., D. Sinha_Roy and A. Thorna-s, _f,ar

Science", Tethnolrryg gA2, T 6 ( l ggg). ( le81).
11. Iirimtrerg, U.1., J. Am. Oil Clmn.
4. Norris, F.A., in Bailey,s Industrial Al anrt Fat pn> &x., S9:2.74 (1982
12. Nagr', I{.. p. Bonsak. ef o.1., fr, Sri"ni,'Twhnolog
durts, 4th edn., Vol. 2 (D. Srvern, ed.), -Refining
and 9O:6,219 ( t9S8).
Bleaching", p. 2gb, John Witey and Sons, New york,
13. tr{ag, T.K.. M.p. Reid,.Ll.S. parenr 4,280,680
U.S.A. (i980).
14. Zschau, W., Bleaching _ Art Opttnt'ieation,
5. Pryor, J.N., J.M. Bogdanor and W.A Welsh, pape
C.hloro, presented at the Tgth AOCS Annual
phgU Retrm)alfrom Edibte Ols, paper Ueeting. iSSZ.
presented at 15. [,oncin, M., et al., in palm UI _
the 78th AOCS Annual Meeting, iSSZ. ' A Major Tyopit:c
Product, Congopalm, Brussels, 1g70.
6. Staal, H.L., J.C. Vis and J.W. Gioeneweg, ti.S. patent -
16. Loncin, M., B. Jacobsberg, Indust.
1,8t2,436 ( 1989). Agn tc. et Alimerd
7. Coultate, T.p., in F@d, 83:19 (196b).
The Chemistrg oJ its Ccmryxr 17 Ros!, H.8., Fette, SeiJen, Arctrichm.ittet
nents, 2nd edn., Royal Society of Chemistry paper_ 65:6, 46i
backs, London, U.K., p.64 (1gbg).
(I 963).
t8.
8. Standard Metlwdsfor the Analgsis of Oils,
Fats o.nd f,V1!e Smet, S.A.. Antwerp, Be{gium, Tech. Butleiit,
15,1982.
Deriuathxs, Z, revised edn., Meihod Z.SO+, gtactcwett
19. Mag, T.K., and M.p. Reid, U.S. patent
Scientific publicarions, Oxford, U.K., lgg7. 4,240,gZZil9eg)
20. Dijkstra, A.J., and M. Van Oopstal, ,t.
9. Riiner, U.E., E. Honkanen. in Rapeseed.,edited
by L.A.
ei.- Ut''CnZi
Appiequist and R. Ohlson, .naibte products &x:. 66:7,1002 (1989).
from 21. Harris, R.D., L. Leving U.S. parent 8,6Z8,228(19i2).
Rapeseed Oil". Elsel.ier publication
Co., Amsterriam, 22. Fahn, R., W. Zschau , possibititiesyor
The Neitrerlands, p. ZSZ (lgTZ). tiiise
Bkorhi,rq Earth, paper presented at the
ci Slmtt
lO. Brimberg,Ij.l., Fette, Seifen, Anstrbhmittel g}:b. 75th
lgl Annual Meeting, lgg4.
AOCS
Deodori zation-Theory and Practice
StanleY C. toft
Johnson-Loft Engineers. Inc. San Rafael, California
Brief HistorY of Deodorization
established in
Tn" n""d to deodorize edible oils was
communitl'want-
the late 1800's when the European
p."a"ce a bland tasting margarine and other
"a-io oil products' luring this same period, the
""S"tuit"
Lin'ited States cottonseed industry was searching-for
;'i;t; remove the unpleasant flavor from alkali
-refined cottonseed oil.
"tl"".r'Eci<stein
is credited with the first steam de-
oaoiUe. in North ,A.merica fcllowed by Boyce' 9arid
{1;s5*son, however, was the first to introduce Euro-
#,"" i""itnoiory in the original Hunt-Wesson high
i""""o. U"tch f,eodorizer. Steam deodorizationvolatileis the
mort prominent method today for removing
'ana
cdor flavor constituents from a relatively non-
-i, i"olote
voiatile edible oii.
th-ese undesirables using distiilation
'uechniques requires high vacuum and high tempera-
tures in the presence of a carrying gas, such as steam'
the amount of
it f'rigft ,ricrlrm serves to ieduceimportantly,
"
strippiig steam required, and most qro-
tect-iitre"oit from oiidation during the process' Other
inert gases can be candidates for striqPing' Mounts
( I ) rSoorted on a German designed, continuous
ioi thin film deodorizer utilizing carbon di-
oxide "t".no*,
as the carrying gas. The 8a! was reused after
regeneration with icfivated carbon. The process
cliims to produce an odorless and flavorless soltrean
oil with alow residual free fatf,y acid content'
Flavor and odor removal is directlyproportional to
the removal of free fatty acid. The third edition of
Bail.ey's Ind'ustri,at Oiii and, Fats (2) states that a
feedsiock oil with an initial free fatty acid content of
0.10% will be stripped of all noticeable flavor and
odor, correspondiir! to a finished, oil free fatty acid of
O.O2-0.04%.Howevei. this is not always predictable' It
has been recently determined that polyunsaturated
oils not properly cooled under stripping steam and
,rcru* can produce an off-flavorproduct. I.lst et aL'
(3) reportea tnat damaged seed oils-can produce low
flivof scores regardless of how well the oil was re-
fined and deodorized.
Proper deodorization will remove peroxides and
volatile secondary oxidation products, such as cer-
tain ketones, aldehydes and other odor compounds'
The object is to produce a fresh, bland tastin-g prq$-
uct thit is basicilly indistinguishable from other oils'
Theory of Steam Distillation
Alion E. Bailey, in his original notes which date back
to 1935, theorized that an-v iri$1'ceride-tra-sed oil con-
taining r,,oiatile rnatter wiit follcw certah lan's of
piiysicl; narnely. Dairon's ia'w of Partiai Pressure anri
Raouit's law- deaii,i-,g '+rich liquid and vapcr
equilibrium.
In equation [1], Dalton's law refers to the relation-
ship where the ielative molar proportion of steam
and volatile matter in the vapor state is proportional
to their partial pressures. It is expressed as the ratio
of moles of Ste;n (S) to moles of volatilecompoun4s
(\r) beine equal to the ratio ofpartial pressure ofthe
it.iam (pis) fdtire partial pressure of t\evolatile corn-
poundi (Pv). Ho*ever, in steam deodorDation, the
iartial piesiure of rolatile matter is very-smailwecom-
can
pared tb steam's partial pressure Therefore.
saythat Ps approiches tlie total pressure as shown i:n
equation [2].
dS _Ps
dv Pv i1l
ds _ P(totai)
dV P!' [21
Raoult's law states that the !-apor pressure of any
volatile compound will equal the vapor pressure, in
pure form, rirultipled by its molar concentration in
itre oii. ThG is expressed in equation [3], where R/ is
the equilibrium pressure, V equals the moles of the
volatil'e compounds and O the moles of non-volatile
oil. As before^, V is very small in relation to O,.so that O
+ V approaches O. Thus we have equation [4].
*- "bh t3l
*=*+ t4l
Vaporation EfficiencY
The vaporization efficiency (E) is expressed in equ-a-
tion [5] as the ratio of partial pressure (h/) to th^e
equilibiium pressure (Pv). In reality, vaporization ef-
fiiieircy atijrr:,pis to heasure ihe corr.pletcness tc
which iteam ls saturated with the volatile matter
when in contac[ with the oil. Bailey, in his original
work. calculated various vapor efficie-ncies. In batch
rlpe deodorizers the values ranged from 0.62-0.73,
using t.0 as uni6'. Both Baiiey {4) and Suliivan (pri-
vate"cornmunicalion, 19?8) point out that in actual
practice, the elltcienc.v ean \:ary w'iih-trav design arrd
ian increase ir: r'alue much higher than unity, as in
the case of ph;"sicai refining oiis containing high free
fatt-v acids. However, w:hen a series of tesis are con-
ducied in a single cieridorizing s,vstem. ih'e vaporiza-
tion efficienq': facior- is a,iequate ftlr relati"'e
measuremenis.
117
 llti
S.C- loJl

f. _ P!,' ABS.
I\ [5] PRES.
mn#lg
6.0 -
..
Through length),inregration and formula substitu,
[lon, we arrive at tlrt..basic e.quation
sleam requirements (S; in deoriorzriti6n.Iti] for,,_p;r.g
tlr
s= Po ln f vt init,i't ppa t.I ,^,
4.5
Er\. FFA)f toJ
4.0
\t',nnu,
3.5
The equation simply states that the theoretical
slgay. required is equal to the total pressure multi_ 3.0
plied by the moles ot non_volatit" oiftiuiaeO
product of the_vaporization efficiency iimes the b, il; 2.5
por pressure of the volatile matter. This quantity,-a_
multiplied by, rhe narural log of the raiio oi molei is 2.0
votatlte components in the undeodorized oil to of 'r.0
moles of volatile compounds ."*uining in the the 1.5 2
ished product. Therefnre, it can U" ii"E"a that hn-
amount of steam required is directly proportionalthe
PErcEl'fr smIpPI.r3 SiEcrrI

the moles of non volarile oil; direcily to

f,iJiortionat to Fig. f. The vaporizarion elficiency of vacuum
steain
the total pressure; inversely p.opoitionJt stripping steam. Ls

\ por pressure of the volatile components; to the va_

and inverse-
11, proportional to the vaporizufior, DEOrcR2T.IG
TEMP. -oc
lFlipt ,callywere "in-"i"n.y.
iltusr rar; rhe ."futionif,ip,
'- .i errtcrencles
por rtrree va_
calculaled based on-the follow_
p".?Terers: V (iniriat),9104 V
ll-g metric lnnurl, O.Oii"J'O,
one ton of oil;I\, 45 Torr at'260rc; ;;A p,!
Torr. Since we are solvingfor (Etv;iu;;;r(sJCit.ip_
ping steam) must be asIig.,ea.toi if-,i, a"*onsrra_
tion, the following values Lre us.ign"a-*i1h their
re_
specrrve vaporzation efficiency (E) calculated:

Stripping Steam Vaporization Efhciency

('., by u,eight of oil) (E)
1.5 0.45
1.0 0.69
0.5 1.38

g brgly re p ress u re is plo tred again r

lil:S-i:.
.rne
1^
I !-|1..
percenr strlpping.steam.-By definifion, the li.igher
s
0.s 1.0
" 1.5 2.0 2.5 3.0 3.5
the vaporization efficiency, thd less steam'is 4.0
at the given operating 'p."rrr."i- ."qu.ii"a PERCENT SIBtpp{.lG STF:A}I
Economicallv
speaking, the. -higher the eificien"i,,-tf.r" l"rJilffi; Fig. 2. The vaporization efficiency of deodorizing
steam is required tempera_
for the large boostei ejectors that tu re VS perccn tage of st ripping steam.
are used to create the vacuum.
,In Figure. 2, the final deodorizing temperature is
p_lo,_r:d against r he prcrcenr strippin! ii""*. Again, it
rs apparenr thar a high r.aporiz^atidn efncienEy cated for each value of (E) where the
require stripping steim it gi""n operating *ili intersect. curves
.less
temperatures. At remperatures b6low One can conclude that, vaporization efficiencies
amount of stripping steam required willZ+b.C iiiE can predict optimum Aeodorbation
asymptotica-lly and is increase give. deodorizer configuratlon-H;;;;Li, i;;;
.not practical. I;ken.ise, one "onaitio";
in actual
jusrify deodorizing oil above 270;C because p._":i]"" nrosr r.aporization efficie;A;irl below 0.6O
:.:nnor
the reirloval of natural tocopherois, which affects oi ti)r 11is cteoclonzing parameters established in this
overall stabilirl' oI t he finisied proauci. -' the denronstration.
. I igure il nlots absolutt i.acuurn againsi ,leodorua_
tion tetnpei.atures. Tliis iiramati""fii'ilu-.trates Commercial Deodorizer Design
et-ti"t.l ,l a iright,r E ,. .rilrt, .'., i,*n *.:*iuo,Li ihe
rlJ)r'ialing ('{)\i\ r',:quiretl itr meei ,n. ui rtuti. Todays cornmercial der;dorizer cciles in
tlies.-'?""Ciii,iri sirapes and sizes.
various
i':irr{ Fig,.rr-t, t. tire iri_,iirriiin .r;,p;;;;;"u*, i.-. ir.,di-
There a*,e serni_coniinuous. contin_
ruous, rhin fiim. verticai. horizontai,
il. i;f.;;,"";;;
 I)ectdorieatiort
-Thanrg
an d Prarttce ll9

DEOmRgI.fS v&uum Syrtrm. 2.5 lo(r

TEMP, . t

E-0.46
s-1.2% LLast qll*
P-2.rlmmHg
E-0.69
s-1.2r(
P-3.0mmHg
T-2600C

E-1.38
s-0.8%
P-3.&nmHg
T-248oc tlalrq lrry

o.g 't.o 2.0 3.0 5.0 7.e ' Stro9n9.lf

Ocodoeung tcy
ABSCmItrE PRESSRS - dg
Fig. 3. The vaporDation ef,rrciency of Ceodorizlrg tempera-
ture \.s absoiute pressirre.
fconoml2?r Cootng Trry

iy, space does not permit revie$, of ali the makes and
models. Bailey (4) probably introduced the hrst com-
Cootrng lrry
mercial semi-continuous deodorizer, known as the
Girdler. This deodorizer became very popular pri-
marily because of its simple design.
During the development stages, it was discovered Co{cctrng Tny
that an oil level less than 100 mm in an open tray was
.,.ery ineflicient. However, when baffles were placed a
short distance above the surface ofthe oil, the vapor-
ization efficiency increased significantly. It u,as ap-
parent that the deflection created by the oil splashing ,,p- ,j _ ,

against the baffles increased the surface to volume

Prodlrt 160
ratio. The oil ler.el was finally established at 600 mm F

with the splash baffle Iocated 60 mm above the oil's Fig. 4. A typical semi-continuous deodorizer.
surface.
Figure 4 symbolizes the semi-continuous concept.
A measured amount (batch) of feedstock is created
in the measuring tank, and is then sequentially heat-
ed, deodorized and cooled by cycling the batches ap-
proximately every 15 to 20 min. This particular dia-
gram illustrates the "thermal siphon" style of heat /5"'
recovery.
Figure 5 illustrates a semi-continuous traywith the
splash or impingement baffles Iocated in the vapor
outiet. The baffles serve to return splash oil created
by the expanding stripping steam as it passes
t.hrough the oil. The shroud showr.l above the baffle
prevents refluxing of condensed fatt1.' acids from
reentering the tra!'and contaminating ti-re freshly de-
oCorked oil.
A iuli.'* continuous deodorizer is illustratetl in Pig-
ure 6. This dia{ram i}lu-strate-c ctiiitiirutiits florv from
lire exiernal deaerator through a vacuurii trim lieat-
er and into the iirst tra;,.at decilorizillg teinperat ures.
'f he t ra;.-s are icientir-ai in srze to the semi r.er-sirin. rr'it It
the addiritin tif veriicai i;ilffies in order ti.i pioriut'e ii
iabl'rintii st.r,le of plug fioiv iF'ig. 7'1. Origl:iaily'. aii
ileating arr.d r:txrlin{ r,\ias a(.c(irnpiis},etri in ihe lra.r,s. t'ig. 5. ,\ s;.lril i'i)nlin:.i,)Lls stiie rlr.r;iiirrl-zt.i trii''
120 SC l1l?

vr4msyrl6.2iTq! L<trtter PrzssrrcDrolr. Frotn ll.0 to 8.0 torr per the'o'

, reti('al stage to ().01 to 0.u torr.
Liqu irl Vttltor Ratio.'llrpic:ll deodorizing tral's c()Il
tairr ve'ry lorv liquid'\'apor ratios a-s conlparetl t<
structured packing.
Caparity. Ihe (c) factor, as defined by Souder ant
Ilrorvn, is the relation of the superficial velocitl
across a tower's cross section and the ratio of thr
Iiquid and vapor density. The "C" factor for a tlpica
deodorizing tra;- *'1ll average approximatell'0.25, a
conrpared to structure packing which can attain lev
' el.'* of 0.{5 or higher. This basicall."- doubles the ma-s
transferefficieltcv.
in 19it6. Bitnersl al. (5) perforn\eci lalrcratory test
using a modified Snyder glass distiliation columu tr
continuously deodorize both hexane extracled ant
super critical carbcrn dioxide extracted soltrean oi
They-produced ar: oii of equivalent qualitl'- to com
mercialll' processed cil. Their data indicated tha
heat bleaching did not occur until deodorizin:
' terp.peratures exceetled 230"C. The Ceodr:rizatiot
experiment paraliels those oiSjoberg. namei;-. 26C"(
1-3 torr \:acuum and l-3lL stripping stearn. iJso c
Fig. 6. A colttinulrtts deodorizer. interesr rr.as the tot.al oii residence tir,e of i-5 mir
Sjoberg's presentaiion illustrated sel-eral tlpes of va
por,,'liquid contact applications (Fig. 8).
The high surface-to-volume ratio of structurer
packing dramatically reduces the overall size of th
column and promotes a more evenll'distributed liq
uid and vapor florv, the latter of rl'hich reduces flor
eddys rrhere fouling or pollT nerization can occur. B€
sides being cost effective from a capital investmen
-L view,point, the moderate reduction in strippin
{!, {' steam. for example, from 1.51)d to 1.0oi,, r€pl'€sents al
ejector motive steam savings of at least 75 kg pe
; metric ton of oil Processed.
Carlson (6) presented a commercial thin film dec
,t
l+ l+
I,*rtl
rT!
tll-i
Frl t-
L _. _lJ
lrl

E]
ra|-based
I
I

trl
Bubble Cap
+
Edrrn -l I'i+
u___,
t
Sieve
I

Fig. 7. -\ corttitrutttts st1-lc deodorizer tra)'.

t+ \,
rll
/'-\ ltt
Hou-ever, rvith tlte emphasis on enersi conservation,
todal''s cleodorizer can be furnished u'ith various ffi ar.)
-r.
L-I-J
t1'pes oi e\ierltal oil-to-oil economizers, evaporative lj_r
E-I-I
cooling and therural slphon lor-rps.
ffi $
lii
-r-
Thin Fitm Deodorization
1-irt' g,ractire oi t"hin ilim vapor liquicl col'itact ha^s
V -.,rl
i,een in tvoiiilir-.n ftir tite past 3{} 1"etrrs. it b€San with Packed Beci Fal1i+g Fiim Rciairng Dis
ii:plilc'enieni of bubble-t'aps it1' siere trals: t'-) ianii(im.
i-i::ncKed i-0lrimns; ttl rvl',a[ is nr.ri''" kntl$'n a-s str'-tctured 1Cc-.-esv ol fr'a-:ava! A.
p.ai: i.;::g. The rezrs<)il irlr iiri.r evoiittkrtr. becornes
{ io-1-iL}u..i. Fig. 8. Sir t5.gics rilrailrr iiquirl cttt-,tal lt6q a;-'plr. liti,ins.
 I)andorizotkn-Thzorg an d Pro.ctice 121

clorizer concept illrrstrated in Figure 9. After proper

deaeration, tire oil is preheated with an oil-oi,l spiral
exchanger and heated to final temperature in a vac-
uun'r trim heater. Approximately 90% of the deacidi-
fication and heat bleaching occurs in this vessel. The
heated oil is then evenly distributed throughout a
structured packed column with approximately 2-4
min of hold up. This concept shows the oil being
cooled by evaporating condensate into ejector motive
steam. This *'ill conserve an additional 50 kg of mo-
tive steam per metric ton of oil processed while drop-
ping the oii temperature below 200'C. The oil is fur-
ther cooled and filtered prior to storage.

Pilot Plant Test for Thin Film

Deodorization
In 1984, Johnson-Loft Engineers, Inc. (San Rafael,
CA), in a jcint I'enture with POS Laboratories in Sas- Fig. 10. A POS packed tower deodorizer.
katoon, Sa-qka"uchewan, Canada, constructed a thin
fitm, packed style, continuous deodorizer that would
operate at 20tl-300 kgr/hr using comrnercial support The feed material is first loaded into deaeration
equiprnent such. as a -"hermal oil heaiing sy-stem. a vessel between 70-90"C. The material is then contin-
u muiriple stage vacuum booster s,'stem. and normal
sieam qeneration. Figure i0 illustrates the flow sche-
uously pumped through an external heat exchanger
rvhere it is heated to final deodorizing temperatures.
malic of ihe process pilot- plant unit. The oil then passes through the frst retention vessel
designed for three levels of retention with or without
stripping steam. From the first stage retention t'essel
the oil is distributed through the first set of packing.
At this point, the product can be directed into an
intermediate retention vessel, where the retention
time is adjustable. For the test data presented. the
intermediate reLention vessel was bypassed. The sec-
ond stage packed section is, in most respects, identi-
cal to the irrst stage. The finished product is then
cooled and discharged.
For the test, approximately 1,500 kg each of com-
mercially refined and bleached soytrean oil, corn oi-l
and sunflower oil was obtained from various U.S. and
Canadian processors. The initial oil analysis is shown
in Table 1. These analyses represent both well refined
and bleached oils.
Table 2 identifies the deodorizating parameters un-
der which the tests were conducted. Due to the limit-
ed amount of feed material, it was necessary to nar-
row the variable parameters to flow, temperature
and stripping steam.
The first stage retention time for soybean and sun-
flower oils remained constant at four min. For corn
oil, a longer retention time was selected. Depending
on feedstock and stripping steam flow rate, the
Fig. 9. A continuous, thin film deodorizing plant with
packed tower hold-up time varied between 2-5 min.
ovaporative cooling. The pressure drop across the packed bed also r-aried
with flow rates. With a constant ejector suction pres-
TABLE 1

Neutralized and Bleached Oil A.nalysis

FFA Clcltir I)I' Phor'phorus Chir-,rcp1,r51

(ir-l Yellcw'Red ileg Kg piim r-,pi*
So.,ieaa il.(); 14 1.2 () :8 {,i.1}5
{-lr.: rr', {}.i.rs ;i6 2.ri I 1.-1 0.+ !j
-iLi n fio *:t'r +t t j I i) 7 1.(l r.15 ().2 fi.!.' I
 \

122 S.C. lnJl

TABI.E 2 TABLE 4
Deodorization Conditions Tocopherol Analysis

Sarnple' Feed Rate Stearn Rate Temperature J^ yd

Oil No. KgiHr % 'C Oil Mgr 1009 }{g,1gg* tr{gil00g
Soybt,an SBl 250 0.5 265 Soytrean
ST]2 250 0.5 255 Neutralized &
SB3 250 1.0 265 Bleached 19.0 M.5 7.5
Corn CRI 250 0.5 265 Deodorized OiI t4.2 47.4 l.L

CR2 250 1.0 265 Percent Retained

CR3 200 1.0 265 in OiI 74.7 87.0 96.0

Sunflorver SFI 250 0.5 265 Corn

Neutraiized & \
s12 254 1.0 265
Bleached 3.3 i6.2 24.3

sure of 2.0 torr, the differential pressure rang€d from

Deodorized Oi] 2.il 18.3 ll-,t
Percen-t Retained
1-3 torr. in Oii 63.4 7t.2
Table 3 presents the deodorized oil ana\sis corres-
ponding to the process conditions tisted in Table 2. Sunficll'er
The finished oil analysis clearly falls w-ithin corrun€r- Neutralized &
ciall-v- accepted standards. The slightly posiiive Bleached 5.C) tr. A1q

percxide values indicaied in Sampte SB L and SB2 can Deodorized Oil 3.0 tr. 35.4
probably be attributed to the Iength of time ( 10 da:si Percent Retained
from the test-runs to the analysis- No additives or in tlii 60.0 G ?4.0
antioxidants were used in the tests. The samples
were sent to an independent taste panel and the re-
sults shown here represent a span of four weeks after ers, fouling rvill not effect lhe operating efficienc5u or
the test runs. All samples were refrigerated and blan- finished oil qualiry.
keted with nitrogen. In summary, the test work and data presented
Table 4 illustrates the retained amounts of toco-
pherols left in the finished oils. Tocopherol is an im- clearly indicates that thin fiIm deodorization is an
portant natural antioxidant and with today's sophis- acceptable alternative to todays practices of tray,
sieve or bubble cap technolos/. Further anall,sis will
ticated consumer, it only seems natural to retain the be compiled regarding the retained oil sample quality
highest ievel of stability without the use of additives.
and published at a later date.
One of our major concerns for using structured
packing, or any packing for that matter, is the ten-
dency to foul when processing highly unsaturated Acknowledgments
oils. After six months of operation, the packing \ras
removed and inspected, and found slightly filmed The refined and bleached oils were pror.ided b.'" CSP Foods,
with polymerized oil. However, none of the channel Canada, and in the Lr.S. by Honeymead Products and the
openings were obstructed. We believe with biannual AE. Staley Company'. A special thanks to POS and their
chemical cleaning associated with liquid oil deodoriz- capable staff.

TABLE 3
Deodorized Oil Analysis

Sample FFA; Color PV Rancimat

oil No. O/
h YeIlow/Red Meg/Kg Hr@ 120'C

Soybean SBI o.o2 3.910.6 0.36 2.8 'l+

SB2 0.01 3.3/0.5 0.18 2.0 E+
SB3 0.01 3.7 /0.5 0.00 3.0 9
1+n
Corn CR1 0.02 9.5,, 1.5 0.00 1.6 ir
CR2 0.0? 9.4,'1.5 0.00 tl
CR3 0.(,1I 7 -1;-1.3R r).00 ;rl
j *.'
S,.:nfiou'er SFI ,() I 'l ,i-, tt.ti (i.oil :o
ctr9 .02 .-1.s,/a).7 ( i.i){} jti :!

:+a
*Rcpresents samples of commerciali]' tiottie.j ,-;ii-
 Ikndarizatiort usry a rrd f>ract.ict' t23
-Tlr

References Product-s,3rd edn., Interscience Publishers, NY. 1964.

/. Am. Oil Ch,en. &r. 26:166 (1949).
1. Baile-v, A.E.,
l. Mounts, T.L.,J..{trt. Oil Chen.,9oc. 60:453 (1983). t
Bitner, 8.D., J P Frederick and T.L. h{ounts, Iliid.
2. List, G.R., C.D. Evans, K. Warner, R.E. Beal. W.F. Kwoi- 63:338 (1986).
ek, L.T. lllack and K.J. Moulton , Ibid. 54.8 ( 1977). Carison, K, Ibid. 65.
3. Swern, D., ed.. Baikty's lttdu-ctrial OiL an.d Fat