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Патент USA US2408455

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2,408,454
Patented Oct. 1, 1946
UNITED STATES PATENT. OFFICE
2,408,454
DECOLORIZING OILS AND AGENTS
THEREFOR
Francis Michael Sullivan, North Bergen, N. J.
No Drawing. Application July 16, 1941,
Serial No. 402,696 -
10 Claims. (01. 2104-62)
2
' 1
This invention relates to the decolorization and
puri?cation of organic compounds of animal and
.
in the art, without departing from the scope an
spirit of the present invention.
vegetable origin, and particularly to the treat
In accordance with the present invention pre
formed soaps, particularly of hydrous character,
ment of glyceride oils and related products and
agents therefor.
Ca are utilized for removal from natural products
such as glycerides, of dissolved solutes contained
The natural glyceride oils vary in character
therein which it is desired to eliminate and of
both with respect to the glyceride present and also
which the color {bodies are particularly exem
with respect to the various dissolved ibodies con
plary. It has :been found that the color bodies
tained therein designated herein by the term
solutes. The glyceride oils are exemplary of nat 10 present in such natural glycerides are collectively
adsorbed by such preformed soaps so that they
ural esters, alcohols and acids which carry vari
may be readily and economically removed from
ous bodies dissolved therein during the prepara
the natural products, such as glycerides, by such
tion of the material from the tissues in which
treatment; the use of preformed hydrous alkali
they occur in nature. The variation in charac
metal soaps is particularly desirable for the ad
teristics of the impurities and color lbodies present
sorption of the color bodies and impurities in
in such natural products has given rise to di?i
naturally occurring fatty materials and that pro
culties in puri?cation and decolorization, particu
cedure and treatment will be used to exemplify
larly due to variation in characteristics of ‘the
- color bodies which are present in glyceride oils,
the present invention.
“
In accordance with the present inventionha
for example.
20
hydrous soap desirably in concentrated suspen
The most commonly used prior art method of
sion in a medium that is miscible with the mate
re?ning fatty materials consists essentially of
rial undergoing treatment, is mixed with such
mixing the fatty material with an excess of alkali,
material to be treated and then separated from
usually a solution of sodium hydroxide, with re
moval of the precipitated material. This opera 25 the latter. The hydrous soap is of such nature
as to- be separable from the material undergoing
tion is frequently followed by removal of residual
treatment. While various types of soaps may be
color by treatment with activated earth and car
utilized, particularly important results are ob
bon adsorptive materials. The chemical treat
tained by the use of the soaps in specially pre
ment involved in the use of alkali unfavorably
affects ?avor, taste and other desirable charac 30 pared condition and several examples are given
immediately below of the preparation of such
teristics in food and medicinal products and also
hydrous soap agents for use in accordance with
results in substantial losses of the glycerides
which are being puri?ed or treated. Further
more, some of the natural glycerides are not sus
ceptible to decolorization by such alkali ‘treat .35
ment.
Among the objects of the present invention are
included the treatment of natural products, par
the present invention.
‘
Example I -
5 parts (by weight) of stearic acid and 15 parts
of oleic acid are added to 60 parts of decolorized
cottonseed oil and the mixture heated and stirred
until the stearic acid dissolves. The temperature
ticularly glycerides in the form of oils, etc., to re
move undesirable solutes, particularly color 40 was adjusted to about 50° C. and 26 parts of a
13% solution (aqueous) of sodium hydroxide was
bodies, therefrom.
‘
.
added gradually with agitation.
’
Other objects include the purification of these
The resulting product is very desirably em
materials without exposure to chemical action
such as characterizes the caustic alkali process.
ployed in decolorizing glyceride oils.
-
Other objects include the production of agents 45
Example II
desirably employed in the puri?cation of such
20 parts of decolorized palm oil fatty acids were
natural products, particularly the glycerides, and
dissolved by heating with 60 parts of decolorized
methods of making such agents.
Still further objects and advantages of the pres
ent invention will appear from the more detailed
description set forth below, it being understood,
however, that this more detailed description is
given by way of illustration and explanation only,
and not by way of limitation, since various
cottonseed oil. The temperature of the mixture
was adjusted to 50° C. and 26 parts of a 13%
solution of sodium hydroxide was added grad
ually with agitation.
This product also can be utilized in the treat
ment of glyceride oils for decolorization and ‘re
changes therein may be made by those skilled 55 moval of solutes from the. natural glyceride oils.
12,408,454
3
.
4
and is not limiting. But the presence of water is
While a variety of soaps can be employed in
accordance with the present invention, the alkali
desirable although alcohol may be substituted at
, least in part, in the formation of the soaps.‘
metal soaps are most desirably utilized produced
The characteristics of the preformed soaps are
from fat acids. The term fat acid is utilized here
in to cover the higher fatty acids Contained in UK also determined for use in the present invention
by the medium in which they are prepared and
natural glycerides such as oils and fats, both of
animal and vegetable origin; The soap employed ‘ desirably the soap adsorptive agents employed in
accordance with the present invention are pro“
should be of such character that it may be sep
duced in situ as a suspension in a desirable me
arated from the treated. oil, but it must also have
the ability to adsorb the color bodies or other deg ‘ jdium.‘ Aqueous media alone are not so satisfac
sirable solutes to be removed from thevglyceride,
tory for'the preformed soaps because of the for
Most desirably an
' oily medium is employed, particularly a medium
' .niation of curd-s or strands.
The properties of the soaps which are thus most
desirable for carrying‘ out the present treatment 7‘ "which is miscible with the oil in which event it
V are readily produced by the use of mixtures of _
fatty acids which should be convertedinto the >
preformed soaps. By the use of solid acids,1-pa'r'-' 13
' ticularly of, saturated character, the separation-or»
_> sh-ouldnotr dissolve the soap. By the production
,rof'the preformed soap in situ in the oily medium,
a concentrated suspension of the preformed soaps
inthe form of small droplets in the oily medium
is first obtained. On standing the droplets usu
segregability of the preformed soaps from ‘the
treated oils is readily controlled, since an increase 20 ally coalesce. In these forms the products are
suitable of usein connection with the‘ present
invention. The soap stock is ?nely dispersed in
the oil under treatment by violent agitation to
providea maximum surface for adsorption of the
in the‘ content of solidacids increases the readi
ness of separation of the soaps from the, oil.‘ ,vBut
theiuse of solid acids alone are not so ‘satisfactory,
anda substantial amount of liquidacid is, desir
color bodies. _ Glyceride oils, therefore, offer a
ably emp-lcyed to give effective solvent action on A
the colored- bodies. The. most preferred type of
preformed hydrous soap composition is, therefore,
one which is produced from ,mixed fatty acids
having the desired'solid and liquid acid content,
the solidv acid desirably ‘being’ saturated and the 30
' liquid acid unsaturated, the proportions of the
acids in the mixture being such as to give ready
also giving ready adsorption of the color bodies
in the oil which is being treated] Generally the
proportions of the mixed acidsnshould be ‘of such
character as to produce a hydrous soap of pliable
character and: the solvent action obtained on the
color bodies is bestrwhen the hydroussoap em—
.
The use of stearic acid for’ the solid acid com
ponent in an amount constituting 25% of the
fatty acid mixture, as in Example I‘, gives an ad- .
s-orptive agent which is practically ideal. -Other 45
proportions may be employed and the ratios of
fatty acids when mixed fatty acids are employed
necessarily depend on the characteristics of the
to decolorize the medium during thetreatment;
butv since the adsorpti've' capacity of the soap is
most desirably employed for removal of the color
' bodies from the crude'glyceridei oil's undergoing
separation of the preformed soap produced from
such acids, from the oil undergoing treatment and
ployed is of pliablevcharacter.
very desirable medium for carrying the preformed
soaps. It is not essential that the oily medium be
decolori‘zed since the Soaps themselves will serve
treatment; a decolorized oily me'd'iumig preferred.
Other media that can be employed include fatty
acids, fatty alcohols of the‘ higher types, and var
ious fatty acid esters "such as ‘ethyl oleate‘, where
the presence of ‘such-media ‘in the oil undergoing
treatment is not-objectionable,Ias for. example,
in the production of paint oils, etc. The amount‘
of oily medium present should ' be‘ sufficient to
cover the soaps and the vproportions given Ex
ample I arevery desirable. Other ratios, for ex
ample, would include 5 parts ste'aricjto 15‘ parts of
oleic with 30 parts of the oil as given in Example I.
De‘s'lr'abl'y the" medium used to carry the by]
dreu's soap products or the" reaction between' the “
alkali and acid is usually the same‘ or ‘similar to
the products resulting from the hydrous soap
acids being used’. Whenvstearic acid isused for 50 puri?cation treatment in order to avoid the in
deduction of ally undesirable‘ material into the
the solid acid component, it enables the lowest
?nal'pi‘oduct. This is particularly true in con
amounts of solid; acid toebee employed. Other
nection‘ with the production of “food products,
solid acids would generally’ ‘beused inhigher
' ,suchas, salad oils. 'Where, the treated“ glycerides
ar'eto'beused for purposes where the introduce
acid can be used satisfactorily. When the ratio
of stearic to oleic reaches 50:50,fthe product is 55 tion of foreign oils is immaterial, then the me
dium may differ from that .of the oil resulting
somewhat hard andinot as satisfactory for ad~
quantity. A mixed acid containing 40%of stearic
sorption purposes. The liquid acid present should
as indicated above, desirably be unsaturated. and
from ‘theipuri?cation treatment, To, avoid free
tures of acids can be'utilized as indicated and
The following examples illustratethe u'tiliza;
tion'of ‘such preformed scans in decolorization of
alkalL'the ‘hydrou’ssoap' concentrate is prepared
with an excess of, acid and such excess of acid,
generally should not, be less than 30% depending ,
T
on the type of ‘solid acidv employed. Various‘ mix 60 although small,is desirably present. ‘A
mixed solid acids and mixed liquid acids can'also
be employed. Other exemplary compositions are
90% lauric acid with 10% oleic acid and 40%
glylceride oils. ‘
'
.
Example-III
I
‘
e
~
.
palmitic acid with 60% oleic vacid, both of which 65
Crude cottonseed oil was washed with’ about
produce satisfactory operation.‘ Oleic acid alone
10% of its weight of water at about'iih" C."_The
may be employed at'temperatures of about ~20°
water caused coagulation of a portion of the
C., but the use of individual acid is not so satis
‘solutes: and the water and coagulated solutes were
factory.v
I
'
The soaps produced should desirably be of hy 70 then separated from the oil using a centrifuge.
5.%'by weight ‘of a hydrous soap concentrate pre
drous character and a sufficient amount of water
pared in accordance with Example I were inti
should be present so that the soaps are not too
mately contacted with the oilat a temperature,
hard. The 13% of aqueous caustic soda ‘employed
for
‘example, of about 30°C. by violent mixing '
in Examples I and II is, merely exemplary of the
‘and passage through a restricted opening under
caustic soda concentration that may be employed
2,408,454
5
slight pressure.
6
The soaps were removed from
the oil by centrifugal separation.
‘Corn, soya
bean and peanut oils may be similarly treated.
The initial step of washing with water as given
inthis example may be omitted and the process
content of the soaphas an important in?uence
on its plasticity and hence its effectiveness. By
‘carried out otherwise as set forth in this exam
adjusting one or more of these variables, all of
the 10 to 20 carbon acyclic acids can be used in
the preparation of a workable hydrous soap stock
and most of them can be applied directly with
p18.
out blending but in practice blending is resorted
Example IV
to for optimum results. . Owing to the great num
ber of these acids, a limitless number of blends
Crude cottonseed oil was heated rapidly to
310° C. without agitation and then cooled rapid 1-0 of varying formulations might be used to yield a
ly. A sludge resulted which was removed by
centrifugal separation. 5% by weight of a hy—
drous soap concentrate prepared in accordance
with‘ Example I were put into contact with the
oil at about 30° C. by violent mixing, and passage
through a restricted ori?ce under slight pressure.
The soaps were then removed from the oil by
centrifugal separation.
~
Example V
Crude palm oil was heated rapidly to 300°
C. without agitation and then cooled rapidly. 5%
by weight of a hydrous soap concentrate prepared
in accordance with Example II was violently
mixed with the oil at about 50° C. The soaps
were then separated from the oil by centrifugal
separation.
Example VI
5% of a hydrous soap concentrate prepared in
accordance with Example I were violently mixed
with cocoanut oil at about 30° C. The soaps
were separated from the oil by centrifugal sep
aration.
The procedure given in Example VI is applica
ble also to animal and ?sh oils and by the use
of slightly higher temperatures for tallow and
higher mel ting fats.
Various acyclic acids of from 10 to 20 carbon
atoms may be used in the preparation of the
soaps. However, as pointed out, the mixture of
desirable adsorptive- gel type of soapstock. The
soaps obtained from the mixtures of acids as they
are found in nature in cocoanut, palm and other
glycerides are applicable to the adsorption of
color bodies.
The governing principle in the
_ choice of acid proportions using any combination
of acids is to use su?cient of the harder soap
forming acid to provide just enough solids in
the hydrous soap gel to allow it to be separable
from the oil under treatment Without undue emul
si?cation. The hydrous soap stock must contain
suf?cient solids to provide for the separation, on
the other hand it must contain sufficient of the
liquid hydrous soap component to adsorb the
color bodies.
,
The utilization of preformed soaps in accord
ance with the present invention enables control
of the character of soaps used in the treatment
of the oil and by the use of soap adsorbents in
accordance with the present invention, alkali is
kept out of contact with the oil and in this way
the undesirable effect of alkali, as for example, in
isomerization of cottonseed and palm oils, is elim
inated. Emulsi?cation is also avoided which fre
quently takes place in connection with oils such
as heat treated oils. Any free fatty acids pres
ent in the crude oil undergoing treatment, are
not affected and may be recovered ultimately as
such free fatty acids, for example, by distilla
tion, in a re?ned condition.
Treatment of the
oil undergoing re?nement by repeated contact
soaps should be of such nature that the soap
and removal of fresh portions of the hydrous soaps
formed is capable of being separated from the
provides a maximum of decolorization. The soaps
material being puri?ed without undue emulsi?
used for the second contacting of an oil may be
cation. Emulsi?cation can generally be avoided
used again for a primary contact of a fresh oil
by the use of acids that yield partially solid soaps
prior to disposal.
under the operating conditions. This charac
Having thus set forth my invention, I claim:
teristic varies from acid to acid and depends in
1. The method of treating a glyceride oil con
part upon the length of chain and extent of
taining its natural color bodies to decolorize the
unsaturation.
50 same which comprises intimately contacting said
The acids that may be employed vary widely
glyceride oil with a preformed hydrous alkali
since by blending acids, which by themselves
metal soap of saturated and unsaturated fat
would be inapplicable owing to the hardness of
acids, the unsaturated fat acid constituting at
their hydrous soaps, with acids that yield a softer
least 30% of the soap forming acids, and the
soap, a product can be obtained that is satisfac
amount of saturated fat acid being Sll?'lCieIlt to
tory. Thus certain acids such as lauric, my
produce ready separability of the soap from the
ristic and iso-oleic can be used without admix
oil, the soap being dispersed through the oil in .
ture with other acids. Stearic acid cannot be
?nely divided condition, the'soap being separable
used alone because its soaps are too hard for
from the oil, and separating the soap carrying the
favorable adsorption of the color bodies. Linoleic
color bodies from the treated oil.
acid alone yields soaps that are too softfor
favorable separation from the oil. A mixture of
the two acids, e. g. 30% stearic-70% linoleic,
yields a hydrous soap that is effective. The tem
perature at which a hydrous soap is used, of
taining its natural color bodies to decolorize the
same which comprises intimately contacting said
2. The method of treating a glyceride oil con
glyceride oil with preformed hydrous alkali metal
soaps separable from the oil, the soaps being
course has a bearing on the softness of the soap
formed from saturated and unsaturated fat acids ,
and by working at substantially elevated tem
peratures, for example 80° C., stearic and palmitic
acids which cannot be effectively used alone for
applications at about 30° C. may be used alone 70
30% of unsaturated acids, the soaps being dis
persed through the oil in ?nely divided condi
tion, and separating the soap carrying the color
or in admixture with each other.
bodies from the treated oil.
Correspond
ingly, by working at reduced temperature, acids
can be used which would be too soft to be eifec
tive at normal temperature. In addition to tem
containing at least 25% of saturated and at least '
'
3. The method of treating a glyceride oil con
taining its natural color bodies to decolorize the
same which comprises homogenizing said glyc
perature and fatty acid composition, the water 75 eride oil with preformed hydrous alkali metal
2,408,454
7
8
soaps of a saturated solid fat acid and an un
separable from the oil, and separating the soap
saturated liquid fat acid, the solid fat acid con
stituting at least 25% and the unsaturated liquid
9. The method of treating a glyceride oil con
carrying the color bodies from the treated oil.
taining its natural color bodies to decolorize the
fat acid at least 30% of the soap forming acids,
same which comprises homogenizing said glyc
the soap being separable from the oil, and sepa
eride oil with a preformed hydrous alkali metal
rating the soap carrying the color bodies from
soap suspended in a glyceride oil di?erent from
the treated oil.
that undergoing treatment, the soap being sep
4. A method as set forth in claim 3 in which the
arable from the oil undergoing treatment, and
saturated acid is stearic acid and the unsaturated
10 separating the soap carrying the color bodies from
acid is oleic acid.
the treated oil.
5. A method as set forth in claim 3 in which
10. The method of treating a glyceride oil con
the saturated acid is lauric acid and the unsat
taining its natural color bodies to decolorize the
urated acid is oleic acid.
same which comprises homogenizing said glyc
6. A method as set forth in claim 3 in which
eride oil with a preformed hydrous alkali metal
the saturated acid is palmitic acid and the un
soap of saturated and unsaturated fat acids, the
saturated acid is oleic acid.
unsaturated fat acid constituting at least 30%
7. A method as set forth in claim 3 in which
of the soap forming acids, and the amount of
the saturated acid is stearic acid and the unsat
saturated fat acid being sufficient to produce
urated acid is oleic acid and the proportions are 5
20 ready separability of the soap from the oil, said
parts of stearic to 15 parts of oleic acid.
soap being suspended in a glyceride oil different
8. The method of treating a glyceride oil con
from that undergoing treatment, the soap being
taining its natural color bodies to decolorize the
separable from the oil undergoing treatment, and
same which comprises homogenizing said glyc~
separating the soap carrying the color bodies from
eride oil with a preformed hydrous alkali metal
soap suspended in an oil of the same character 25 the treated oil.
FRANCIS M. SULLIVAN.
as that undergoing treatment, the soap being
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