Patented Sept. 12, 1944
‘
2,357,881
UNITED (STATES PATENT OFFICE
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2,357,881
PROCESS or TREATING GLYCERIDE OILS
Bernard A. Dnmbrow, New York, N. Y., assignor to
National Oil Products Company, Harrison, N. J.,
a corporation of New Jersey
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No Drawing. Application May 13, 1941,
Serial No. 393,187
9 Claims. (Cl. 260-4285)
The present invention relates in general to the
fractionation of fatty materials and in particular
to an improved processof solvent. fractionation of
table and marine oils, including, inter alia, soya
bean oil, linseed oil, cottonseed oil, cod oil, sardine
oiL-tuna. oil, cod liver oil, tuna liver oil, shark
glyceride-containing oils and fats.
It is well known that animal, vegetable and
' of oils are composed essentially .of triglycerides
'1 marine oils and fats are composed predominantly
of oleio, linoleio, linolenic, clupanodonio, licanic,
oil, etc., maybe fractionated. The foregoing class
of triglycerides of the higher fatty acids having
elaeosteric, palmltic, stearic and like fatty acids.
varying degrees of, unsaturation. While the
According-to the process an oil of the fore
natural occurring oils and fats containing tri
going type 'is contacted with a hydroxy solvent of
glycerides of varying degrees of unsaturation 10 the type which is characterized by being a better
have utility, the constituents thereof are far more
solvent for the unsaturated ‘triglycerides than
the saturated triglycerides. The preferred class
valuable in their isolated form. - For example, in
the paint and varnish industries the unsaturated
triglycerides ?nd considerable use. Likewise
many uses are found for the more saturated tri
of solvents includes, among others, alcohols hav
ing 1 .to 3 carbon atoms, such as methanol, etha
15
nol, n-propanol, isopropanol and chlorhydrin.
The solvent or mixture of solvents is ‘brought into
contact with the oil in such a manner as to dis
solve all the oil or only a portion thereof. The
unsaturated triglycerides from a mixture of satu
temperature of contact may be varied to suit the
rated and unsaturated triglycerides.
20 conditions at hand. In some cases it is desirable
to heat the oil and solvent to dissolve all the oil
A speci?c object of the invention is to pro
in the solvent. Whether complete dissolution is
vide an improved process of producing‘ drying
effected or not, the oil-solvent mass is allowed to
oils from marine oils.
stand, whereby two layers are formed. In cer
Other objects of the invention will in part be
25 tain cases, especially where all or a major portion
obvious and will in part appear hereinafter.
of the oil is dissolved in the solvent, chilling aids
In accordance with the'invention a mixture of
glyc'erides.
'
The general object of this invention is to pro
vide a simple and improvedv process of separating
and/or accelerates the formation of two layers.
saturated and unsaturated triglycerides of the
The foregoing class of hydroxy solvents is char
higher fatty acids, such as are found in animal,
acterized by selectively dissolving out the un
vegetable and marine oils, is contacted with a
hydroxy organic solvent in the presence or not 30 saturated triglycerides from a mixture thereof
with saturated triglycerides. These solvents also
of heat. The solvent oil mass is then allowed
possess the property of preferentially retaining
to separate into two layers, one layer containing
unsaturated
triglycerides in solution when the
a predominating portion oi’ the unsaturated tri
temperature of a solution of both saturated and
~ glycerides and solvent and the other layer con
unsaturated triglycerides is decreased. It may
taining the major portion of the saturated tri
35 be seen, then, that the degree of dissolution in
glycerides present in the oil originally.
the solvent of the oil treated may be varied. In
The invention accordingly comprises the
any event the temperature of dissolution of the
several steps and the relation of one or more of
oil and the subsequent layer separation step. is
such steps with respect to each of the others
controlled to give a solvent solution of a fraction
thereof, which will be exempli?ed in the process 40 rich in unsaturates. The solvent-oil ratio may
hereinafter disclosed, and the scope of the in-=
be varied from 1 to 12 parts of solvent to one
vention will be indicated in the claims.
part oi oil.
In carrying out the process of the invention
For a fuller understanding of the nature and '
any suitable composition containing a mixture of
objects of the invention, reference should be had
saturated and unsaturated glycerides of the
to the following examples which aregiven merely
higher fatty ac’ds may be employed.
These I
glycerides may be either partially or completely
esterified, i. e., they may be composed of either
, mono, di or triglycerides or a mixture thereof.
- However, inasmuch as the natural occurring oils 50
contain substantially no mono or‘ diglycerides,
to further illustrate the invention and are not to
be construed'in a limiting sense.
Example I
92 grams of cod liver oilxdissolved in 150 cc.
n-propanol and solution chilled to —17° 0.,
whereby two layers were formed and subsequently
separated. The original oil had an iodine value
the treatment of triglyceride mixtures and par
ticularly natural oils and fats is preferred. In
of 150 and the solvent extracted oil gave an
accordance with the process of the invention
naturally occurring oils, such as animal, vege 55 iodine value of 166.2.
2
2,8o7,881
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vent in which are dissolved glycerides relatively,
Example II
94 grams of cod oil admixed with 150 cc. ethanol
‘ rich in unsaturates.
2. A process of treating a fatty oil to obtain
therefrom a fraction rich in unsaturated triglycg
erides, which comprises contacting the oil with
and cool to room temperature whereby two layers Cl a monchydroxy unsubstituted alcohol containing»
and heated in a pressure vessel to 85° C. to form
a clear solution. Solution was allowed to stand
were formed. The oil remaining in the solvent
layer had a higher iodine value than the origi
nal oil.
Example III
layers.
10
450 cc. of sardine oil were admixed with 450 cc.
of 95% isopropanol and heated to 62° C. after
which the mass was cooled to below 29° C., where
upon two layers formed. .The layers were sep
arated and the isopropanol layer was found to
contain an oilfraction rich. in unsaturates.
The fractions rich in unsaturates as‘ produced
in accordance with theprocess of this invention
have been found to be admirably suited for use
as drying oils. The degree of step up in iodine
value of the solvent fraction over and above that
of the original oil is dependent on the particular
oil treated as well as the'solvent and conditions
employed. The solvent may be removed from the
unsaturated triglyceride fraction by any suitable
method such as distillation.
1 to 3 carbon atoms, cooling the mass to induce
the formation of two layers, and separating the
'
Since certain changes may be made in carrying
out the above process without departing from
the scope of the invention, it is intended that
3. A process of treating, avj?sh oil to'recover ,
therefrom a fraction rich in unsaturated triglyc
erides, which comprises contacting a ?sh oil with
a monchydroxy unsubstituted alcohol of from 1-3 ' '
carbon atoms, permitting the .mass to stand
whereby two layers form and separating the
layers.
'
v
4. A process of treating a ?sh oil to recover
~ therefrom a fraction rich in unsaturated triglyc
erides,v which comprises admixing a ?sh oil with .
a monohydroxy unsubstituted alcohol or from 1-3
carbon atoms, heating the mixture to dissolve at
least a portion of the oil, cooling the mass to
form two layers and separating the layers.
5. A process of treating a fatty oil to obtain
therefrom a fraction rich in unsaturated triglyc»
erides, which comprises contacting the oil with
isopropanol, cooling the mass to induce the for-w , '
mation of two layers and separating the layers. ‘
6. A process of treating a ?sh oil to recover
a fraction rich in unsaturated triglyc
all matter contained in the above description 30 therefrom
erides, which comprises contacting the fish oil.
with isopropanol, permitting the mass to stand,
whereby
two layers form, and separating the
Having described my invention, what I claim
layers,
‘
shall be interpreted as illustrative and not in a
limiting sense.
‘as new and desire to secure by Letters Patent is:
-7. A process of treating a ?sh oil to recover
1. A process of selectively separating a frac
therefrom
a fraction rich in unsaturated triglyc
tion which is rich in unsaturated glycerides from
erides,
which
comprises mixing the ?sh 011 with
a material containing said glycerides in admix
isopropanol, heating, the mixture to dissolve ‘at
ture with a vmore completely saturated glyceride,
least a portion of the oil, cooling the mixture to
wh'ch process comprises contacting the material
form two layers and separating the layers."
40
with an organic solvent, said solvent beinga
8. A process of treating a fatty oil to obtain
monchydroxy unsubstituted alcohol of from l—3
' therefrom a fraction rich in unsaturated triglyc
carbon atoms, which at a low: temperature is
erides, which comprisescontacting the oil with
relatively immiscible with the saturated glyc
ethanol, cooling the mass to induce the forma
eride, the temperature of treatment being above in tion or two layers and separating the layers.
about minus ‘20° C., the ratio of solvent and the
9. A ‘process of treating a fatty oil to obtain
temperature being below that of complete mis
therefrom
a fraction rich in unsaturated triglyc
cibility with the glycerides, separating the two
erides,
which
comprises contacting the oil with
phases while they are both in liquid state, one
propane], cooling the mass to induce the forma
containing primarily undissolved glycerides rela
tion of two layers and separating the layers.
tively poor in unsaturated glycerides and contain
ing some solvent and the other consisting of sol
’ BERNARD
DOMBROW. /