Nov. 6, 1951 S. E.

FREEMAN ET AL 2,573,897
SOLVENT EXTRACTION OF WITAMIN A FROM FISH LIVER OIL
Filed Jan, 29, 1947

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Patented Nov. 6, 1951 2,573,897
UNITED STATES PATENT OFFICE 2,573,897
SOLVENT EXTRACTION OF VITAMINA
FROMFISH LIVER OL i
Stephen E. Freeman, Pittsburgh, Pa., and Stewart
W. Gloyer, Milwaukee, Wis, assignors to Pitts
burgh Plate Glass Company, Allegheny County,
Pa., a corporation of Pennsylvania
Application January 29, 1947, Seriai No. 725,108
9 Claimis. (C. 16-8)
2 " ??
/
*The present invention relates to separation of tain patents such as U. S. Patents 2,380,418,
concentrates of oil soluble vitamins such as vita 2,380,414, 2,380,410, and 2,347,460 it has been pro
mins A and D (if D is present) from certain vita posed to obtain concentrates of vitamins from
min bearing oils and has particular relation to vitamin bearing oils by first heating a mixture
the separation of such concentrates by means of s of oil and a solvent such as isopropyl alcohol in
order to dissolve the oil in the solvent and then
organic polar Solvents. cooling the solution to a temperature of 0 to
One object of the invention is to provide a -70° C. in order to effect separation of a large
simple arid inexpensive process of obtaining con portion of the glycerides from the solvent. The
centrates of vitamin. A suitable for use in cap O vitamins were thus substantially concentrated in
sules and pills from vitamin A containing oils the solvent. These patents disclose processes
which normally are of too low concentration which apparently require batchwise operation.
satisfactorily to be so employed.
A second object is to provide a process of ob This is true because in Some instances the oil is
completely dissolved in the solvent. Obviously
taining vitamin A concentrates which is simple 5 countercurrent flow of the components in solu
and relatively inexpensive to operate. tion is impossible. In other instances, the oil
A third object is so to treat a glyceride oil con containing vitamins and
taining vitamins soluble therein as to effect sepa under conditions of refluxthe solvent are admixed
for the solvent. Coun
ration of the oil into a plurality of fractions one tercurrent flow of a refluxing Solvent and oil
of which is greatly enriched in vitamins. 20 would be highly impractical if not impossible.
A fourth object is to provide a process of the
foregoing type, the application of which does not Such System would also necessitate use of sol
vents having very low solvency for the oil. Ob
result in substantial loss of the vitamins in the viously, the techniques involved were slow and
oil.
A fifth object is to provide a process of obtain 5 expensive.
In certain patents such as U. S. 2,200,390 and
ing concentrates of vitamins from glyceride oils 2,200,391 procedures are disclosed for the frac
containing vitamins in low or moderate concen
tration with selective polar solvents which can tionation of certain glyceride oils to obtain con
with most solvents be operated at temperatures centrates of the more unsaturated components
by liquid phase extraction with organic polar sol
near or not much below normal room tempera
ture. 30 vents. The procedures as outlined in the patents
A sixth object is to provide the process of ob areInnot applied to the concentration of vitamins.
taining concentrates of oil soluble vitamins by posedU.toS.wash Patent 2,090,739 to Tischer, it is pro
solvent extraction which involves dissolving in liver oil or thealike vitamin bearing oil such as cod
with a polar solvent such as
the solvent a minimum amount of the fatty
glycerides of the oil and a maximum amount of 35 furfural in order to remove Odor, color, and taste
constituents from the oil without substantially
the vitamins contained in the oil.
These and other objects of the invention will reducing the vitamin concentration of the oil re
be apparent from consideration of the following maining as a raffinate.
The present invention contemplates a process
specification and the appended claims. 40 whereby oils containing vitamins such as vita
It has heretofore been proposed to obtain con
centrates of oil soluble vitamins such as vitamins mins A and D are obtained in high concentration
A and D from vitamin bearing glyceride oils such from vitamin bearing oils even of low or moder
as fish liver oils' by various methods. Compli ate vitamin concentration by a simple process of
cated and expensive chemical procedures have liquid phase countercurrent extraction with or
been proposed for the purpose. For example, it 45 ganic polar solvents such as are disclosed in the
has been proposed to saponify the glycerides in above mentioned Patent 2.200.391 to obtain a
the oil with an alkali and then to extract the major portion of the vitamins in a minor extract
vitamins from the soaps by means of hydrocar portion of the total oil treated.
bons. The technique involved was complicated 50 reference For a better understanding of the invention
and expensive. It has also been proposed molec may now be had to the accompanying
ularly to distill concentrates of vitamin A from drawing in which the single figure diagrammati
the oils. The methods of distillation employed ratus cally illustrates a suitable embodiment of appa
for the purpose are highly technical and require for obtaining concentrates of vitamins by
the application of very high vacua. The tech continuous liquid phase countercurrent extrac
nique is expensive, especially where large vol 55 tion of oils such as fish liver oils. In the draw
umes of the more plentiful fish liver oils of low or ings, like numerals refer to like parts throughout.
moderate concentration constitute the original number In the practice of the invention any one of a
source of vitamins and is likely to result in some of selective polar solvents may be em
degree to degradation of the vitamins. In cer ployed to obtain a fraction of glyceride oils which
 2,578,897
3
are greatly enriched in vitamin A simultaneously, ished in vitamins and 4. will contain in solution a
vitamin D, if present, will be similarly concen minor amount of the solvent employed.
trated. In general, the solvents will be organic Appropriate polar solvents can usually be se
polar solvents such as those disclosed in Patent lected by a simpletestinvolvingshaking up a con
2,200,391 to Stephen E. Freeman. In the patented - templated polar solvent with a small amount
process the solvents are employed to separate of the oil to be extracted in a test tube or a
natural glyceride oils such as inseed oil, soy separatory funnel or other suitable laboratory
bean oil, or the like, non-vitamin bearing oils, apparatus and observing if the oil and the Sol
into fractions upon the basis of unsaturation of vent at a definite constant temperature tend to
the glyceride molecule. In the patented process Separate into two liquid phases so that the ex
as well as in the present process, it is required O tract or solvent phase will contain 2 to 25% of the
that the solvents, in addition to being polar, be Original oil. Concentration of vitamins in the
but partially miscible with the oil at the tempera extracted oil can easily be determined by well
ture of operation so that the oil-solvent system
can be separated into two liquid phases from 15 known chemical, physical or biological tests.
The following table illustrates the application
which the Solvent can be evaporated. The ulti of such test to a large number of polar solvents.
mate or final extract phase will comprise most These tests were conducted upon dogfish liver oil
of the Solvent and a minor proportion of the oil in
which vitamins A and D are highly concentrated. containing
gram. The
about 10,000 units of vitamin A per
same test obviously could be conduct
The final raftinate oil constituting most of the 20 ed upon other vitamin bearing oil such as cod
glyceride and especially most of the more satu liver oil, soupfin shark liver oil, halibut liver oil
rater glyceride will be correspondingly impover and others:

Per Cent Units Vit. Algram

Sovent Solvº. Temp., Vitamin
????????of| ?????????? | ** Extract Rafi
Diff.
Hydroxy:
Met ?obol------------------------------------- 7.0 10:1 39 18, 180 9,520 8,660
Ethyl alcohol, 95%------ -|| 16.6 || 8:1 | 61 || 14,800 || 8,700 || 6, 100
N-Propyl alcohol------- 78.0 6:1 12 10,800 8,000 2,800
sopropyl alc”, 91%----- - 14.0 6:1 25 12,500 9,090 3,410
Ethylene Glycol---------- - 14.4 6:1 51 10,000 9, 100 900
Hydroxyl lene
EY Ester:glyco------------------------------------ 20.4 3
8:1 51 10,500 9,300 1,200
Ethyl
Ethyll ????:
lactate 3.3
249
3:1
5:
44
23
16,660
13,330
9,090
8,700
7,570
4,630
Methylactate
HydroxyiCarbonyl:
Methylbutanolone.--
9.5 5:1 57 25,000 7, 140 17,860
Diacetone alcohol----------- 43. 3:1 32.5 10,500 9,500 1,000
Hydroxyl Ether: 34.5 3:1 24 11,110 7,700 3,410
Methyl ceilosolve (h-methoxyethanol) -------------- 10.6 5.5: 40 18,180 9, 520 8, 660
Ca???ve (b-ethoxyethanol).----------- 58.6 5.55:1 0 11,800 5,000 6,800
33. 3:1 8 12,500 8,300 4,200
8.6 6:1 5l 11,770 9,500 2,270
4.1 4:1 61 22, 200 8,700 3,500
Hydroxyl, Other: 20.8 2:1 17 2,500 8,000 4,500
beta-ethoxy-ethyll glycolate.-- 6.8 2.5:1 80 13,330 9, 100 4,230
Furfluryll alcohol.--...-- 6. 4:1 40 16,660 8,330 8,330
Carboxyl: Acetic acid.
Aciul Anhydride: Acetic 22. 7.5:1 32.5 5,400 7,700 7,700
Ester: 7.6 6:1 41.5 22, 200 8,700 13,500
Glycol diformate----------------
Glycol diacetate---- 5.3 8:1 60 11,770 9,090 2,680
Ethylidene diacetate.-- 150 5:1 51.5 16,000 7, 140 8,860
12.5 5:1 24 16,660 8,000 8,660
486 5:1, 31 10,800 7,700 3, 100
- - -- - 19.8 5: 8 15,400 8,000 7,400
Ester,Diethyl oxalate-------------------------------------
Carbonyl: ? 39.6 3.33:1 24 12,500 9,090 3, 410
Methyillevulinate-----------------------------------
Ethyl ovulinate.-- 9.5 6:1 14 17,000 8,000 9,000
Mett:: acetoacetate 34.6 6:1 14 11,800 7,500 4,300
-0------------- 3.5 5: 22 28,570 9,090 19,480
Ethyl acetoacetate 9.3 5:1 | 60 | 15,300 8, 700 | 6, 700
Ester, Ether: Methylce 3GE 17. 8 5: 23.3 13,330 7,700 5, 630
Ester, Imido: Ethyl N-methyl carbamate 27.5 3: 8 12,500 7,900 4,600
Ester, double Bond: Ethyl maleate------- 32.3 2:1 29.4 12,090 8,300 3,790
Ester, Double Bond, Ether: Mothyl furoate 6.3 1.1: 33.5 15,700 8,560 7,140
Aldehyde: ---.
Acetaldehyde-------------------------------- 29.6 3:1 -13 13,330 8,330 5,000
Aldohyde, Other: 40.3 6:1 16 11,700 8,300 3,400
Furfural.--------------------------------------------
Furfural--5%. O. 17.7 8:1 17 18, 180 6,660 11,520
Crotonaldehyde------------------------------------- 19.2 8:1 | 62 | 13, 330 |
8, 700 | 4, 630
Carbonyl: 36,0 2:1 --2,500
?5 10,800 8,300
Acetone--------------------------------- 58.5 4:1 4 11, 100 7,150 3,950
Acetone--3% HO--
Diacetyl--------- 169 4:1 8 14,300 8,000 6,300
Acetonyl acetone 22?? 4:1 21 13,300 7,700 5,600
Carbony Amido: Dim 17.0 6:1 25.7 16,660 8,300 8,360
Ether, Carbonate: Beta-methoxyethylic 122 6:1 24.6 16,660 9,090 7,570
Nitro: 6. 2:1 40 7,850 8,550 9,300
Nitromethane-------SLLLLS SSLSSSLS S S SLSL qSqSqS SS SSL Sq SS S LS SL TBSL LSLLSLSLLTLLLLSS S
D0-------- 20 9:1 25 19,050 9,090 9,960
Nitroethane--------------- 9, 8 9:1 60 16,600 8,800 7,800
Amino, Double Bonds: Aniline 17.6 3:1 25 13,330 8,000 5,330
Nitrile:Acetonitrile------------- 16.2 4:1 15 10,500 7,700 2,800
Inorganic: 88 6:1 53 22,220 9,090 13, 120
Phosphante:Liquid SO---------------------------------- 4.7 4:1 -7.5 22,000 9,000 13,000
Trimethylphosphate-------------------------------
Triethylphosphate-------------------------No opom op op op w
5.9 5:1 | 65 | 14.300 | 9,300 | 5,000
Binary Solvents: 37.0 5:1 24,13,330 8,330 5,000
1 part naphtha.---------- 10.0 9:1 25 18, 180 7,410 10,770
l part naphtha.----------
parts mononethyl ether 11.5 6:1 || 41.5 | 20,000 * 7, 140 | 12, 860
 ?,578,897 _ ?? ??
5 6
The following constitutes a partial list of Sole contain in solution most of the vitamins A and
of the more favored polar solvents that can be D (if D is present) and is taken off near the bot
employed in the operation of the processes herein tom of the column through Illine 11. It likewise
described: may be stripped of solvent in a still Such as 8
Methyl lactate and the solvent vapors may be passed through
Methyl carbito conduit 9 to condenser 2 for recovery. The
Methyl acetoacetate liquid solvent is drawn of through lines. 22 and
Acetonitrile 6a to storage tank 2 where it is combined with
Methyl alcohol that from condenser 6.
Monomethyl ether of ethylene glycol () The yield of extract product oil from column
Furfury alcohol O taken in line 20, based upon the original feed
Acetic acid * ? oil, will depend upon the mode of operation of
Glycol diacetate the system as hereinafter more completely de
Acetonyl acetOne scribed. It may constitute the final extract prod
NitrOmethane uct of the system in which case it will constitute
Dimethyl formamide about 2 to 25% of the original oil in which most
Furfural or a large proportion of the vitamin A preferably
is concentrated. Some of this extract oil, e. g.
It will be apparent that in each instance where 10 to 95%, stripped, or at least partially stripped
the oils and the polar solvent to be tested were of solvent may be recycled or refluxed through a
but partially miscible, there was some degree of conduit 24 to a zone in column 0, a short dis
concentration of the vitamins as determined by tance above the bottom thereof. Usually the ex
appropriate tests for vitamins in the extraction tract phase so recycled will contain no more than
phase, that is the solvent predominant phase. 50% solvent. The proportion may be much
In Some instances the concentration was very 25 lower. Assuming that the Selective Solvent is
pronounced indicating that these solvents would furfural which is of a density of 1.1598, while
be especially suitable for use as solvents in a fish liver oil is...about .925, evaporation of Solvent
Counter-current extraction in accordance with reduces the density of the resultant Solution SO
commercially feasible methods hereinafter out that the reflux will tend to rise through the
lined. Counter-current extraction is, of course, 30 downwardly flowing extract solution. The reflux
Susceptible of giving much higher degrees of vita may even be completely stripped. This reflux in
min concentration than the batch extractions. creases the vitamin content in the lower Zones
Suitable apparatus for commercial operations of the column and thus produces an enriched ex
as diagrammatically illustrated in the drawings tract product. The refluxing action may be
includes a column O which constitutes a verti 35 termed “rectification.” In order to control the
cally elongated extraction Zone and which may ratio of reflux to extract product taken, Suitable
be appropriately packed with rings, saddles, baf control devices are provided. The simplest form
fles or the like. The column preferably is fairly of such device of course would involve valves Such
long, e. g. 50 ft. or more in the extraction zone as valves 27 and 28 in lines 20 and 24. If valve
and it may be provided with suitable means for 28 is closed there will be no reflux and the extract
maintaining a temperature gradient between the
top and botton. Such device may comprise a oil will pass to storage in a container 29; Or if
number of jackets, e. g. upper jacket Oa and certain alternative procedures are followed, as
lower jacket fob having inlets Oc and outlets hereinafter will be described, it may be passed
Od through which a suitable heating transfer on through line 20a controlled by valve 20b to
medium may be circulated. Other heating or a column 3, which constitutes a second verti
cooling device such as coils in the column for cally elongated extraction Zone, for further ex
circulating a transfer medium, electrical resist traction.
ance heaters, or the like may also be employed. The column 3 can in the alternative be:
The mixture from various positions in the col (a) Eliminated from the system, in which in
umn may also be withdrawn, passed through a stance it is possible to obtain adequate yields of
heat exchanger of to either cool or heat the mix extract containing a concentrate of vitamin A
ture and finally be repumped back into the by use of (1) reflux through line 24 and, or (2)
column at any desired position. Oil constitut by maintaining the upper part of the column at
ing a Source of vitamin A or A and D, is brought a higher temperature than the lower part, such
in as indicated at f from a storage container effect being attained by circulating heat transfer
a to a Zone approximately at the middle of media in jackets foa and Ob or by feeding in
the column. An appropriate organic polar sol solvent at the top of the column at a higher tem
vent Such as furfural is introduced from con perature than the feed oil or by other methods,
tainer f2 through line 2a into column O a short such as by circulating column solutions through
distance below the top of the column in such external heat exchangers, such as the heat ex
manner as to provide a Zone 3 in which the changer of where the liquids are cooled or
separation of the liquid raffinate from the solvent heated as may be required:
can take place. (b) A small extract (2 to 25 %) of high vita
The raffinate consisting mainly of a fraction min concentration can be taken and the raftinate
Of the original oil impoverished in vitamin A is Can be re-extracted in column. 3. The second
drawn off through a line 4 at the top of the co extract can be recovered as a third product or
lumn. It may be delivered to an appropriate stillit may be returned to the original feed. The sec
5 where it is stripped of dissolved solvent. TheOnd raffinate is a final product of use in stock
vapors of solvent are then recovered in a con 70 feed or other purposes.
denser 6 and the liquid solvent is recycled to (c) A moderate or large (e. g. 25 to 75%) ex
storage 2 through a line 6a. Certain alterna tract can be taken from column O and a corre
tive modes of treating the oil will subsequently be spondingly reduced raffinate taken preferably as
described. a final relatively low vitamin potency product.
The extract oil contained in the solvent will 75 The extract of a higher vitamin content than the
 2578,897
7
original oil can be re-extracted in column 3 and
the second extract taken as the highest vitamain
concentrate of the System while the Second raf Line m.
finate is recovered as a third product Or may be
recycled to the feed of column 0. 20
29a
2,800
5,840
Assuming that one of the alternative methods
b or c is employed, solvent from tank 2 is in Conditions of operating column 31
troduced into the column 3 by lines 3 la at a
point slightly below the top of the latter. The Oil used, raftinate oil from column fo, line 29a
raftinate of the column is taken of at the top 10 Solvent used, anhydrous furfural
through line 32 and passes into still 33 where Solvent ratio, 10:1 based on rafflinate oil feed rate,
solvent medium may be stripped off and and line 29b
passed on to condenser 34 for recycling through Oil reflux, none
line 34a to solvent storage. Dependent upon the Temperature, 96-100° F.
mode of operation of the system, solvent free 5 It is to be observed that in this example the
raftinate may pass through line 35 to storage in Second column (3) is operated at a substantially
container 36 or, alternatively, it may be returned higher temperature than the first (O), thus to
through a line 35a, having a control valve 35b to obtain the desired vitamin concentrate from the
the oil supply container fa. It will be apparent
that since the rafflinate is usually low in dissolved 20 first column. The reflux of Example 3 or the
temperature gradient of Example 4 could be aps
solvent, it may not be necessary to strip it before plied in this example,
recycling it as feed oil to column 0. The inven
tion, therefore, contemplates recycling of raf Per Cerat Taken
finate from column 3 With Or without stripping Products Yield Linefron Units Wit.
Algma.
in still 33, to column O directly through line
in conjunction with Original feed oil. Extract.----- 40.3 49 2,360
Extract from column 3 which may be a final Raffinate- 59.7 35 2,100
vitamin concentrate Or a product suitable for re
cycling and mixture with the original feed oil to In the above series of extractions three final
column fo dependent upon whether alternative 30 products are produced, the yields and potencies of
b or c is employed, passes off through line 3 to these being given in the following table:
still 38 where the Solvent is stripped and de
livered through line 39 to condenser 40 and is Products Per Cent Taken from Units Wit.
finally returned to storage through lines 4 and Yield Line Algm.
34a. The extract oil is drawn of through line 42.
It may go in its entirety to storage 43 or a part Extract-----------------------
2nd Extract------------------
17.4
33.2
20
42
24,800
2,360
may pass through a line 44 to provide reflux to 2nd Raffinate-- 49.4 35 2,100
lower zones of column 3f. This reflux in part Original Oil------------------------------------------ 10,000
controls the vitamin content of the extract of
column 3. The ratio of reflux may be controlled If it is desired the second extract may be
by valves 45 and 46 which can be opened or closed blended with the original feed oil and be re-ex
to determine the ratio of reflux of the extract. tracted in column 0.
Instead of passing the extract oil of column In Example 2 the System is operated in accord
3t to storage or to reflux in the column, all or a ance with alternative c as above outlined, the
part of it can be sent through line 47 to the feed 45 raffinate from column O constituting a final low
storage container a for return to column fo. vitamin product, the extract of column 3 con
Reflux through line 44 is again permissible. stituting the high vitamin product and the raf
Valves 48 and 49 in lines 42 and 47 then deter finate of column 3 being returned to the feed
mine the course of the extract oil from the col oil of column fo. The conditions of operations
umn i. 50 Were aS follows:
In the Specific examples appended hereto are EXKAMPE 2
illustrated conditions of operation of the columns Oil used.--Dogfish liver oil containing 10,000
O and 3 for use with dogfish oil containing units of vitamin. A per gram.
about 10,000 to 20,000 units of vitamin A per gram
and with furfural as a polar solvent. Example 1 55 Conditions of operating column 10
illustrates the operation of the System in accord Solvent ratio, 10:1 based on oil feed rate
ance with alternative b in which a small extract Solvent used, anhydrous furfural
fraction of high vitamin content is taken from Oil reflux, none -
column 0, this constituting the final vitamin 60 Temperature, 93° F.
concentration as obtained from the System. The
extract from column 3 is in this instance en Per Cent Taken from Units Vit.
ployed as a part of the feed oil and the raftinate Products Yield Line Agm.
from column 3 is employed as the final low vita
min product of the system. 65 Extract-----------------------
Rafinate---------------------
50.7
49.3
20
29
22,000
2,260
EXKAMPILE 1
Oil used.--Dogfish liver oil containing 10,000 Conditions of Operating column 31
units of vitamin. A per gram. Oil used.-Extract oil from column fo, lines 20
70 and 20.
Conditions of operating column 10 Solvent used, anhydrous furfural
Solvent ratio, 8:1 based on oil feed rate Solvent ratio, 8:1 based on extract oil feed rate,
Solvent used, anhydrous furfural line 29
Oil reflux, none Oil reflux, none
Temperature, 58-60 F. . 75 Temperature, 67 F.
 2,573,897
9 10
it is to be observed that in this example the Conditions of operating column 10
Second column (3) is operated at a lower tem Solvent used, naphtha Saturated furfural
perature than the first (O), thus to obtain the Solvent ratio, 8.3:1 based on Oil feed rate
lower ratio of extract as the high vitamin con Oil reflux, none
centrate from the latter. Naphtha reflux, 0.13:1 based on oil feed rate
Column temperatures:
Per Cent Units Wit. Top, 148 F.
Products Yield Line Algm. Bottom, 48 F.
Extract. 28.2 42 34,000 O
Raffinate- 78 35 7,460

In the extractions in this example three prod 14.2 1,500

85.8 8,060
lucts are produced, the yields and potencies of
these being given in the following table:
The raffinate in this example could be used as
Per Cent Uits Wit. feed oil in Examples 1, 2 or 3 or could be admixed
Products Yied Line Agm. with fresh oil therein and re-extracted to recover
20 a second extract of improved vitamin A concen
1st Raffinate------------------ 49.3 29a 2,260 tration. Such second extraction may or may not
2nd Raffinate-----------------
2nd Extract------------------
36.4
14.3
35
42
7,460
34,000
be preceded by stripping of the solvent in the raffl
nate. In Example 4 it will be apparent that the
The second raftinate may be blended with the original temperature of the system at the top of the
feed oil. 25 column could have been Somewhat higher than
given in the example though, of course, it should
In the third example column 3 was cut out not be so high as to induce excessive Solution of
of the system and column O was operated with the particular oil being treated. Similarly, the
a reflux to obtain in the single column a high temperature at the bottom of the column may
Vitamin extract and a low vitamin raftinate. 30 be reduced below the value given in the example
The conditions in the system were as follows: but again it should not be So low as to excessively
reduce the fraction being taken off. Preferably,
EXAMPLE 3 the extract will constitute 2 to 25% of the feed
Oil used.--Dogfish liver oil containing 10,000' Oil.
units of vitamin A per gram. 35 The extract solutions of oil as obtained in the
foregoing examples may be further extracted with
Conditions of operating column 10 a paraffinic hydrocarbon, e. g. a naphtha approxi
Solvent used, anhydrous furfural smating a heptane to decane in average molecular
weight. By such treatment the glycerides and
Solvent ratio, 20:1 based on oil feed rate leav?
-4t(
yitamins are washed from the polar solvent,
Oil reflux, 0.5:1 based on oil feed rate /ing most of the free fatty acids, coloring matter,
Temperature, 70-71 F. Odor, and taste constituents concentrated in lat
ter Solvent. In Such proceSS, the naphtha may
Per Cent Units. Wit. be in variable proportion, but 14 to i based on Oil
Products Yied Line Algm. 45 feed rate is satisfactory. The extraction may be
effected counter-currently in a column at a
Extract----------------------- 28.8 20 33,000 temperature of about 70 to 75° F. These values
Raffinate--------------------- 71.2 29 1,700 are quite appropriate for dogfish liver oil. Some
degree of variation for other oils to compensate
In a further example illustrating the practice for differences in solubility of other vitaminifer
of the invention relatively high concentrations of ous oils may be desirable.
vitamins in the extract oil obtained from column In the specific Examples 1 to 4 inclusive the
0 was accomplished by maintainance of a tem oil treated was dogfish liver oil containing vita
perature gradient between the top and bottom of min A in the proportions indicated. It will be
the column. In this process the temperature 55 obvious that various other Vitaminiferous oils
gradient may be attained by use of heating or notably of the fish liver type such as tuna fish oil,
cooling elements at appropriate points in the col halibut liver, shark liver oil or other oil may be
umn, for example by means of jackets Oa and substituted. With such substitutions some vari
Ob r by use of the heat exchanger of, which ation in the temperature values given may be
may be supplied with an appropriate heated 80 desirable since each of these oils has its own
?????? or by the employment of Solvent at a tem Solubility characteristics.
perature above that of the feed oil. In the ex Similarly, it will be apparent that various other
ample the Second column was not employed. It is . polar solvents such as those included in Table A
obvious that a temperature gradient may also be 65 may be substituted for the furfural of Examples
maintained where a second column is employed 1 to 4 inclusive, the solvents being employed to
to re-extract either the raffinate or the extract extract dogfish liver oil or any of the other oils
from column 0. The conditions employed where herein enumerated, the temperatures of solu
a temperature gradient was maintained and bility of the oils found in any of the selective sol
vents being determined by the methods herein
furfural was employed as the polar Solvent are 70 discussed. The ratio of solvent to oil may be ap
illustrated by the following examples: proximately those values given for purpose of
EXAMPLE 4 illustration in Table A and the temperatures may
also be the same or similar to those tabulated.
Oil used.--Dogfish liver oil containing 17,400 Though, as in the case of furfural, wide varia
units of vitamin A per gram. 75tion of ratios of solvent, for example in the range
 - 2,578,897
11 12.
of 3 to 30 parts of solvent by volume for each the zone whereby to obtain a cool extract of
part of vitamin bearing oil is contemplated. glyceride oil and solvent which is highly enriched
Similarly, the temperatures of extraction are sus in vitamin A and a warm raftinate which is coro
ceptible of considerable variation, though the respondingly impoverished in vitamin A, draw
temperature in the zone from which the final ing of the raftinate at the top of the zone and
extract is taken should not be so high as to take the solution of solvent and extract at the bot
out more than about 25% or less than about 2% tom of the zone and evaporating the solvent to
of the oil upon the basis of the original feed oil. obtain the concentrate.
A range of 10 to 80° C. covers nearly all contin 2. A process as defined in claim 1 in which the
- gencieS. 10 solvent is furfural. .
The vitamin depleted raftinate oil from the ex 3. In a process of separating a concentrate of
traction can be used as a source of vitaminA, e. g. vitamin A from a fish liver oil containing said
in chicken or cattle feed. vitamin, the steps of continuously flowing one
The products as obtained by the foregoing pro volume of said oi upwardly and flowing three to
cedures will be of relatively high vitamin A con s thirty volumes of organic polar solvent, which
centration as compared with the oils from which is but partially miscible with the oil, downwardly
they were derived. This concentration will vary through a vertically elongated zone, the tempera
somewhat dependent upon the vitamin. A con ture in the zone being within a range of 10 to
centration of the Original oil. 80°. C. and being sufficient to effect solution of
. These products in most instances are suffi 20 25 to 75% of the feed oil as an extract in the
ciently high in concentration for their use as solvent, collecting a liquid raffinate phase of oil
vitamin A concentrates such as are employed in impoverished in vitamin A at a point above that
filling capsules. However, if desired it is per of introduction of solvent, continuously with
missible further to treat the oil in order to obtain drawing the raffinate, collecting the liquid extract
still higher concentrations of vitamins. For ex
ample, the extracted oil containing a very high of an
oil in solvent, continuously drawing if off as
extract phase at a point below that of intro
concentration of vitamins may be suitably Saponi duction of the oil, evaporating solvent from the
fied with alkalis such as sodium hydroxide, potas extract phase, passing the oil from said phase
sium hydroxide or the like and made up into upwardly in countercurrent flow through a Sec
aqueous alcoholic solutions from which further 30 ond vertically elongated Zone of downwardly flow
concentrations of vitamins can be extracted by ing partially miscible solvent, the Zone being
means of appropriate selective solvents Such as maintained at a temperature to obtain a second
petroleum hydrocarbons. It is also permissible extract solution of oil in solvent and a second
to distill of concentrations of vitamins from the raftinate of oil containing some solvent, collect
extracted oil, by So-called molecular distillation 35 ing the second extract Solution at the bottom of
in which the extracted oil is subjected to distilla the zone, drawing off said solution, evaporating
tion under very low vacuum and in proximity to of the solvent to obtain the desired concentrate
a cold surface in such manner that the vitamins of vitamin A and recycling the second raffinate
distilled without actual boiling of the oil. These phase by admixing it with the feed oil to the first
methods of concentration are outlined in the text extraction Zone.
book, Chemistry and Physiology of the Vitamins 4. A process as defined in claim 3 in which the
by H.R. Rosenberg. Solvent is furfural.
An advantage of preliminarily extracting the 5. A process as defined in claim 3 in which
vitamin A bearing oils with polar solvents in ac the solvent is furfural, the second zone being op
. cordance with the provisions of the present in erated at a substantially lower temperature than
vention before subjecting them to chemical treat the first.
ment or to molecular distillation resides in the 6. In a process of obtaining a concentrate of
fact that it is possible greatly thus to reduce the vitamin. A from a fish liver oil containing said
proportion of oil requiring such drastic treatment vitamin, the steps comprising flowing one vol
as involved in the chemical separation of Vita O ume of the oil upwardly in intimate contact with
mins or the molecular distillation. The overall three to thirty volumes of downwardly flowing
. . expenses of the operation are thus reduced to a Organic polar solvent which is but partially
substantial degree. Moreover, there is less de miscible with the oil at temperatures of 10 to
composition of vitamins by reason of the drastic 80°C., the Zone being at a temperature adapted
treatment. The raftinate fractions are excellent 55 to obtain a liquid extract solution of 25 to 75%
ly adapted for food purposes such as stock feeds, of the oil in the solvent, drawing off the liquid
or even for human consumption where a a Source extract Solution of oil and solvent at the bottom
of vitamins of low concentration is desired. of the ZOne, evaporating the solvent from the
It will be apparent to those skilled in the art extract Solution, then further intimately counter
: that the forms of the invention herein illustrated currently contacting the extracted oil with polar
are merely by way of examples and that nu solvent in a second elongated zone to obtain an
merous modifications may be made therein with ar overall extraction of about 15% of the oil, then
out departure from the spirit of the invention or evaporating the solvent from the resultant liquid
the scope of the appended claims. extract phase to obtain an extract product which
We claim: SS is greatly enriched in vitamin A as compared
1. A process of obtaining a concentrate of with the Original oil.
vitamin A from fish liver oil containing said vita 7. A process of obtaining a concentrate of vita
min which process comprises passing the oil up min. A from fish liver oil which process comprises
wardly in countercurrent flow through a verti flowing one volume of the oil upwardly through
cally elongated zone of downwardly flowing Or O three to thirty volumes of downwardly flowing
ganic polar solvent which is partially miscible organic polar solvent which is but partially
therewith, the oil-solvent mixture in the upper miscible with the oil at temperatures of 10 to
portion of the zone being maintained at a sub 80 C., in a vertically elongated zone at a tem
stantially higher temperature than the Solvent perature to obtain an extract yield of 2 to 25%
containing dissolved oil in the lower portion of 7s of the original oil, continuously drawing of a
 2,578,897
- 3 4.
liquid raftinate of oil impoverished in vitamin A reflux liquid upwardly in said fractionation zone
at the top of the zone and an extract solution to contact and rectify said downwardly flowing
of solvent and 2 to 25% of the original oil at extract phase; maintaining the rate of flow
the bottom of the zone, the concentration of of Said reflux liquid to produce at some point
vitarin A in the oil of the extract solution be within the fractionation zone a reflux flow rate
ing at least twice as great as the original oil, in the range of 10 to 90% of the rate at which
evaporating the solvent from the extract solution extract oil is withdrawn from said fractionation
and returning 10 to 90% thereof to said Zone at Zone; maintaining furfural introduction at said
a point below that of introduction of the feed furfural inlet at a rate in a range of 3 to 30 vol
oil and above the point of withdrawal of the ex 10 unes of furfural to one volume of charge oil;
tract solution. and recovering a vitamin concentrate product.
8. A process as defined in claim 7 in which the from Said extract phase,
Solvent is furfural. . STEPHEN E. FREEMAN.
9. A continuous process for preparing a vitamin STEWART W. GLOYER.
A concentrate from a charge oil which is a fish 15
REFERENCES CTED
liver oil containing vitamin A, by fractionation
with furfural at a temperature within a range of The following references are of record in the
10 to 80° C., said process being carried out in a ver file of this patent:
tically extended fractionation zone having a
furfural inlet and a raftinate phase outlet near 20 UNITED STATES PATENTS
the upper end, an extract phase outlet near the Number Name Date
lower end and a charge oil inlet in the interme 2,090,738 Tischer ------------ Aug. 24, 1937
diate portion of said Zone, which process includes 2,118,454 Schaafsma, --------- May 24, 1938
the steps of: continuously introducing Said charge 2,248,619 Freedman ---------- July 8, 1941
oil and said furfural into a vertically ex ** 2,347,460 . Buxton ------------ Apr. 25, 1944
tended fractionation zone having a furfural inlet 2,380,418 Dombrow ---------- July 31, 1945
and a raftinate phase outlet near the upper end, 2,394,968 Van Orden -------- Feb. 12, 1946
an extract phase outlet near the lower end and - FOREIGN PATENTS
a charge oil inlet in the intermediate portion of
said Zone; separately withdrawing extract and 30 Number Country Date
raffinate phases from said extract phase outlet 220,697 Great Britain ----- Aug. 14, 1924
and said raffinate phase outlet respectively, said 560,146 Germany ---------- Sept. 29, 1932
extract phase Constituting about 2 to 25% of the OTHER REFERENCES
Original feed oil and having a temperature in
the range of 10 to 80° C., separating furfural 35 Rosenberg, Chemistry and Phys, of the Vita
from at least a part of Said extract phase to pro mins (1942), page 60,
duce a reflux liquid having Substantially lower Chemical and Engineering NeWS (1941), vol.
density than said extract phase, and flowing Said 19, page 624.