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Патент USA US2406249

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Patented A". 20, 1946
’ Ivan A. Partentiev, Nanuct, N. Y.
No Drawing. Application November 25. 1943,
~ Serial No. 511,704
This invention relates to the recovery of valu
_ able materials from ?sh viscera‘and tissues.
More particularly, it relates to the separation of
vitamins from these sources.
This application is a continuation-in-part of
my application Serial No. 448,648 ?led June 26,
(cue-11) _
days at 'l0°-80°v F. This approximates room tem
peratures in the .tropical regions where these op-.
erations are most likely to be carried out. The
' temperature is then raised again to about 98°F.
and after ‘a short time. oil will be found to .be
separated as a surface layer.
After digestion, the large volume 0! 011 form
ing the top layer andtransparent aqueous hy
In the commercial processing of food ?sh tor
the market, the entrails are usually discarded or, ' drolysate forming the lower layer may be sepa
at best, are converted intb low-grade ?sh meal. 10 rated from the solid residue by decantation or ,
siphoning 011. Oil or fat associated with the un
. With some of the larger ?sh such as certain
digested residue may be recovered by a ?ltration
types of the shark, the liver is utilized to recover
operation in which the mixture oi fat and undi
, oil containing vitamin A and little or no vitamin
gested residue on the ?lter is heated to about
D, but the rest of the viscera is discarded. ' The
37-40" C. (somewhat higher for some species of
methods for recovering the vitamin oil from the
?sh). With su?lciently complete digestion, the
liver are usually‘ cumbersome and costly. The
oil associated with the residue ?lters very easily
discarded ‘viscera or entrails not only contain I
‘through soft ?lter paper. During this ?ltration,
substantial quantities of vitamin A but are also
the undigested residue on the ?lter paper be
_ good sources oi.’ vitamin D and some of the vita
min B components.
20 comes relatively dry and this accelerates the sep
aration of the oil from it. The ?ltrate, on stand
It is one of the objects of the present invention
ing, separates into two sharply de?ned layers
to provide a simple and inexpensive method for
with the oil ?oating on top of the watery solu
the utilization of ?sh Iviscera and tissues as a
tion. The oil is easily separated from the aque
valuable source of fat-soluble and water-soluble
25 ous material by decantation or by the use of suit
It is a further object to provide a method for
the recovery of the vitamins from fish viscera
and the like by means which will preserve such
It is' a still further object to provide a meth
for the treatment of ?sh viscera and the like
which is suiiiciently simple to permit operation
at the ?sheries or on ?shing boats and thereby to
avoid shipment to special processing plants.
able separating devices based on the principle
of a separatory funnel. ,The recovery of this
oil by ?ltration through soft ?lter paper is a sim
ple procedure which eliminates the necessity of
adding alkali and thereby permits substantially
complete recovery of oil without impairing the
vitamin content. The several portions of oil and
aqueous iractions'recovered as ‘described, may
be combined or may be handled separately.‘ The
It is still another object to provide a process , oils are very transparent, of pale yellow color,
and form very little ‘sediment on storage.
which can be applied to the separation 01' fats
By the digestion of shark liver in accordance
and water-soluble components from waste ?sh
with the method described, a yield of oil was ob- . 1
tissues containing the same.
tained which represented about 45% on the basis
These and other objects are attained by sub
jecting the raw viscera-and/or tissue, in an acid 40 of the weight of the raw liver. The potency of
this oil ranged from about 8000 to 10,000 I. U. 01"
i?ed aqueous medium, to the action of an acid
vitamin A per gram of oil. This is the same po
acting enzyme at moderate temperatures. The
tency ‘as is obtained commercially by the in
process may be illustrated more speci?cally by
volved manuiact
g processes commonly used.
the following examples.
The liver oil obtained by the digestion process is
Example 1
very stable when digestion is carried out between
pH 1.5 and 2.0. Several samples of such oil
Fish liver is minced by means of a mechanical
stored for a period of over 1 year without preser
grinder and sui?cient hydrochloric acid is added
vative, in white glass bottles, and opened a num
to bring the mixture to an acidity of approxi
of times, nevertheless showed no signs of be
mately pH 1.5-2.0. Hog pepsin or its proteolytic '
coming rancid. Tests carried out on the oil
equivalent in fish pepsin is added in‘ an amount
stored as just described, showed that the vitamin
of about l‘part by weight of pepsin to about 1700
A content of the oil remained substantially con
parts by weight of liver. This mixture is warmed
stant during storage. One sample of oil, when
to between about 90°-100° F. for about two to
three hours and allowed to stand for about three 55 bottled, had 8,962 I. U. oi’ vitamin A per gram
' ,-
and the same oil, stored in the white glass bot-r
tles, without preservative, still had 7,584 I. U. of
e?iciently. Furthermore, the muscle tissues'of
certain species of ?sh, such as eels, are rich in
vitamin B and the like and by utilizing the pres
ent method, it is possible to recover such vitamins.
vitamin A per gram after 6 months; The. poten
cies of oil set forth above were determined col- ,
orimetrically according to the Carr-Price method
without saponiflcatlon.
The aqueous ?ltrate contains several vitamin‘
Two thousand parts of old, salted tuna ?sh liver
B components. After digestion of four di?er
ent samples of shark liver in-the same manner
> was ground in a meat chopper, diluted with wa-'
ter to about 20,000 parts and the mixture was
as Just described, it was found that one cc. of the 10 .adjusted to pH 1.5 by the addition of concené
clear ?ltrate or hydrolysate contained the fol
lowing values of vitamin B as expressed in mi- ‘_
crograms per cc.:
.trate'd hydrochloric acid.] Seven parts of pepsin
dissolved in a smallamount of water was added
and digestion was carried on for two days at ‘a’
temperature of ‘about 37° C. At the end of this .
Ribo?avin _____________________ -_ 2.56 -- 2.86
Nicotinic acid ____ -_'____‘ _______ -___ 9.75 -13.3
period some oil had'qseparated and ?oated on the
top of the aqueous liquid and‘ was recovered by
Pantothenic acid ___________ __~.'_'__ 1.09 - 1.68
Biotin ____________________ __i.._.___ 0.163- 0.213
- decantation as‘ in Example 1.v The fatty sub
stances assoclated with the undigested solid resi- _
due, were separated by ?ltering the mixture at _
The aqueous hydrolysate may be concentrated
to a small volume or may be dried to a powder.
The concentration may be carried out in a suit
able vacuum drier until a semi-solid paste is ob
r‘ooinv temperature. During the ?ltration, some of
the oily material solidi?ed but was melted again
by heating to about 37° C. About 400 parts of
tained. By drying in open pans at about 50° C.
crude fat were obtained. The pure oil was easily .
for about 3-5 days, a substantially completely _ , extracted from the crude fat by mixing the lat
dry material may be obtained. A convenient
ter with an equal or double amount of ether. the
method for obtaining a dry powder is that in 25 ether solution being separated from the residue
which the pasty material obtained in the vacuum - by decantation or ?ltration. The ether was evap- ;
drying is frozen and the frozen product dried
orated and the yield of the oil indicated that'at
under vacuum. The pasty material contained
least 50% of the crude mt was oil, or about 10%
22.58% solids and had the following vitamin B 30 by weight of oil based on the weight of the origi
ues: .
nal salted liver. The, extracted oil contained
Micrograms per cc.
about 118,480 vitamin A units in each gram. The
vitamin content of the oil obtained by the di
Pantothenic acid ....... ..; ____________ -_ 186.2
-Nlcotinic acid _____ -'_.._'_ _______________ _'_
gestion method agreed very closely with that
found in oil obtained by extraction methods, thus
A dry, powder obtained from tuna ?sh liver by
indicating that the digestion step did not cause
the described method contained, ‘per gram of pow
der, the following vitamin B values:
any substantial loss of vitamin.
Ribo?avin _-
The aqueous ?ltrate or hydrolysate obtained in
separating the crude fat in the ?rst filtration was
Micrograms '40 found to contain the following values of vitamin
150 ,
B components as expressed in micrograms per 1
______________________ -_ 12.7
p‘ cc. of ?ltrate:
Pantothenic acid
Nicotinic acid ________________________ __ 37.5"
While the oil obtained as just described is gen
erally clear, it has a tendency to become slightly
cloudy, especially on cooling. .When the oil is
cooled to about 32° K, it solidi?es as an opaque
mass. However, I have found that the oil may
be further purified by treating it with solid mas
Ribo?avin- ___________________________ __ 10 a
Nicotinic acid .... __- _________________ __
Pantothenic acid _.._‘ _____ _._' _________ .._‘__ "1.12
_________ __.._'_ ________________ --
On the basis of the original liver, these vitamin
B components were present in the following
nesium lactate in the proportion of about 1 to 60 amounts as expressed in milligrams per kilogram >
of liver:
10% by weight. based on the weight of the oil
to be treated. More speci?cally, as illustrative.‘
Ribo?avin ____________________________ __. 140
I'may add 5% of the magnesium lactate powder
‘ to the oil after it has been separated by decan
f tation or otherwise as described._ The mixture
is then agitated by shaking, stirring, or the like,
iwfor a short period of time and the magnesium
Nicotlnic acid _________________________ __
‘Pantothenic acid -__-__--..'_ _____________ __
Example 3
i lactate powder is removed from the oil by ?ltra
Fish entrails, obtained from the commerci
tion. The oil is then found to be brilliantly 01881‘.
?sh-dressing process, were ground in a meat chop~
Dale yellow in color and to have but slight odor.. 60 per and enough hydrochloric acid was added to
, This oillremains clear on standing and, while it' _ bring the pH to about 1.8. In order to speed
:1 -_ solidi?es /at low temperatures, when the tempera
the digestion. one gram of pig pepsin was added for
1 ture is raised the solid melts to form the clear Y every three
of entrails. Digestion was
‘ ‘oil.
carried on at 37° C. for 1-3 days. At the end of
This method may also be used on liver of other
this. Period. the fat and associated undigested -
types of mu than shark. e. g., tuna, halibut, cod.
‘ 1 blue?sh, mackerel, etc. Other organs than the
1 liver may be treated in substantially the same
manner to obtain compositions containing vita
' residue were separated by ?ltration from the W8
_ tery ?ltrate.
The acidity of the watery ?ltrate obtained after
digestion of the entrails was adjusted to pH 3
1 mins as well as other fat-soluble components such 70 to prevent acid corrosion in drying. It was then
‘ as hormones.
The viscera and livers of many
small ?sh are impractical‘as sources of vitamins
‘ in the usual processes for recovery of the same
1 but, by utilizing the present method, these or-
concentrated about 20 times ina vacuum dessi
cator until it turned to‘ a semi-solid paste. This
pasty material was dried to powder by freezing
and then drying under vacuum/ while in_ the frozen
gans and tissues may be‘ treated e?'ectively and 75 state. Alternatively, the pasty material may be g
' 2,400,249
placed in suitable’ trays in a drying oven or the
like and the dry product there obtained may be
ground to powder.v The ?sh meal thus obtained
contained about 12% nitrogen and represented
for long periods of time without the addition of
It should be noted that the bulk of the diges-v
tion takes place at the comparatively low' tem
. peratures not exceeding about 100° F.‘ By proc
about 8-10% of the weight of raw entrails; One
essing the viscera or the like at such low temper
gram of the ?sh meal obtained from mackerel
atures, higher yields of vitamins are obtained,
entrails contained 16.1 micrograms ribo?avin, 80.5
micrograms pantothenic acid and 140 micrograms ' since elevated temperatures tend to, decompose
the vitamins. The temperatures of 70°-80° F. are
nlcotinic acid. Fish mealsimilarly obtained from '
approximately equivalent to room temperatures
mixed entrails of bass, ?ounder, porgies, eel and
in many of those sections where the ?sheries
weak-?sh contained per gram of ?sh meal, 19.8
micrograms ribo?avin, 21.8 micrograms panto
are located and hence, by the present process,
‘ thenic acid, and 97.0 micrograms nicotinic acid.
the major portion of the operation may be car
ried out at or not greatly above room tempera
Instead of concentrating the watery ?ltrate as
described, I may mix tricalcium phosphate with 15 tures. Naturally, this simpli?es the procedure
and apparatus required and is obviously highly
phosphate will adsorb most of the vitamin-con
taining materials and may be separated from the
water. By using larger amounts of the phosphate,
desirable from a commercial standpoint. 'Mor‘e
speci?cally, there is provided a simple and in
such ?ltrate in greater or lesser amounts.
expensive method for obtaining high-grade oil
and other vitamin .products at the fisheries on
a pasty mass may be’formed which quickly and
a largenscale and in good yield. These processes
easily dries to a powder. Since the tricalcium
' are especially valuable since they salvage abun
phosphate is a desirable constituent for poultry
dant‘waste materials.
foods and the like, its use in this connection serves
The enzyme digestion process utilized herein.
the double function of concentration or drying
and as a constituent of thepoultry food. Simi 25 appears to stabilize the oil in such a manner that
the oil may be allowed to stand, even in clear
larly, absorbent silica or other absorbent mate
glass containers, for long periods of time with
rials may be used in place in the calcium phos
out developing rancidity or losing its vitamin
potency. No preservatives are necessarycwith the ‘
The fat associated with the residue from the di
gestion of the entrails contains a considerable 30 oil obtained in accordance with the present in
vention. -The liver oils of commerce, previously
proportion of vitamins A and D and may be re
available, were of such composition that it was
covered as described by heating the residue and
found necessary to store them in amber-colored
or opaque containers. Even then, such oils tend
the undesirable residue will remain on the ?lter. 35 ed to become rancid and to lose their vitamin po
,?lteringvit, .while' warm, through soft ?lter paper
by which operation the oil will pass through and
solvent is then removed by distillation from. the
tency so that many substances have been sug
gested for use as preservatives. These precau
tions are not necessary with oils obtained as de
scribed herein. Another advantage of the oil ob
of various types of ?sh vary from about 3—20% I
contains practically no free fatty acid.
Another method which may be used is to extract
the fat from the undigested residue by the use
of ether or some other suitable solvent and the
extracted oil. The oil obtained from the entrails 40 tained by the digestion method is that the oil
based on theweight of the raw materials. This
Nutritionally, liver and other visce'ra proteins
I oil varied from about 3,000 .to about 13,000 U. S. P.
rank high as a source of essential amino'acids.
The solids recovered from the aqueous solution
units vitamin A per gram of oil.
‘ _
The oil may be mixed with more or less of the
meals obtained from the watery ?ltrate described
resulting from the digestion of ?sh livers are, ' .
therefore, not only a source for the vitamin B '
factors butv they also contain substantially allthe
to give a better product for chicken feed or the
nutritionally essential amino acids originally
like. Alternatively, the oil may be mixed with
present as constituents of the viscera proteins.
the watery ?ltrate vbefore it is dried or in one of
While some of the aqueous ?ltrates obtained
the intermediate stages of drying.
from the digestion process as described above may
In place of hog pepsin described in the speci?c
be rather dilute as regards solids content, theyv ,
examples, it is frequently more convenient to use
may be concentrated in any known manner where
the ?sh stomach juice and/or the ground stom
due precaution‘ is taken to avoid decomposition
ach tissue secreting or containing pepsin, avail
able at the ?sheries. Of course, equivalent 55 of the vitamin components of the solution. Vac
uum concentration at low temperatures is e?ec
amounts of the ?sh pepsin are used in place of
tive and, for certain purposes, spray drying is es
the hog pepsin. When entrails are used, they
‘pecially convenient. Where the vitamin B con
usually contain sufficient pepsin for the digestion
tent of the hydrolysate is to be used to enrich some
but more may be added if necessary or desirable.
Other proteolytic enzymes which are active under 60 other material, such as a chicken feed or the like,
acid conditions may be substituted but, for most
purposes, pepsin is more readilyavailable. The
acidity of the mixture during the digestion period
the hydrolysate may be mixed with the desired
substances and the whole is then subjected to
spray drying or a similar operation.
Suitable other changes and variations may be
may vary somewhat from pH 1.5 to about pH 5.0. 65 made in carrying out the invention without de
It is desirable that a low pH be maintained during
parting from ‘the spirit and scopethereof as de
the digestion process in order to prevent bacterial
?ned in‘ the appended claims.
- action and to prevent rancidity. A pH of 1.5-2.0
1. The proces which comprises preparing anv
represents an optimum condition for the temper
atures employed.‘ Where the pH is less acid than 70 aqueous suspension of comminuted ?sh viscera
, at about pH 1.5, adding a small amount of pepsin
about 3.0 it is preferable to add an antiseptic.
to the suspension, maintaining the suspension at
temperaturesbetween about 70°-100° F. until the
orable for retaining the activity of the vitamins.
oil separates and ?oats to the surface, removing ’ Before further puri?cation, the digested livers
in the acid medium at pH 1.5-2.0 can be stored 75 the acid liquid from the solid residue and sepa-- -
Q The acidi?cation of the liver suspension is fav
. 9,406,949
rately recovering the oil and a vitamin B-con
a’ concentrating treatment to recover a concen
‘ ‘ taining aqueous solution from the acid liquid.
trated vitamin product.
. .
10. A concentrated vitamin-B_containing prod
2. A process of recovering vitamin-containing
materials which comprises subjecting ?sh viscera
uct' containing water soluble vitaminstoi fish vis
cera and water soluble peptic-digestion products
in an aqueoussuspension to the digestive action‘
of pepsin at a pH voi! aboutdl.5 and at tempera
of fish viscera, including acid salts of protein
tures not’substantially exceeding about 100° F.‘
digestion products.
11. A dry vitamm-B containing product con- ‘
until’ oil separates from the aqueous suspension,
taining in a concentrated form water soluble
and separately recovering from’ the acid digestion
product the vitamin-containing oil and the vita-. 10 vitamins of ?shviscera and soluble peptic diges
min-containing aqueous solution.
tion products of fish viscera, including acidv salts _
of protein digestion products”
' 3. A process of recovering vitamin-containing
> Y
12. A process of recovering both vitamin-con
taining' oils and water ‘soluble vitamins from ‘fish
materials which comprises subjecting commi
nuted ?sh viscera in an aqueous suspension to
the digestive action of pepsin at about pH 1.5 15 entrails containing pepsin which‘comprises add
ing ‘acid and subjecting the entrails to digestion
- and at temperatures not substantially exceeding
with their contained pepsin under acid conditions
about 100° F. for about two dayaseparating the
and without further addition 0! pepsin and sub-_
> acid liquid material from the solid residue, tur
jecting the still acid digestion product to a sepa
ther ‘separating the acid liquid material into an
' oily fraction and an aqueous fraction anddry 20 ration treatment to separate vvitamin-contaimingv
oil and an acid aqueous vitamin-cong ex-__
ing the aqueous traction.
, .
tract therefrom, which aqueous extract-contains
4. A process of recovering vitamin-containing
water soluble vitamins and other water soluble
materials which comprises subjecting commi
digestion products of the entrails including such
nuted- ?sh viscera in an aqueous suspension to
therdigestive action of pepsin at about pH 1.5 as constituents in ‘the form of their acid salts;
13. The process of recoveringv both vitamin
and ‘at temperatures not substantially exceeding
containing oils and water-soluble vitamins from
‘aboutlOO" F. for about two days, vremoving the
?sh viscera which comprises subjecting ?sh vis
' acid ‘liquid from the solid residue and separately
cera to the digestive action oi~pepsin under acid
recovering vitamin-containing oil and vitamin‘-~
‘containing aqueous solution from the liquid. _ v
30 conditions and subjecting the still acid digestion
product to a separation treatment to remove vita
5. A process of recovering vitamin-containing
materials which ‘comprises subjecting commi-. - , min-containing oil and an acid aqueous vitamin
containing extract thereirom,<which aqueous exi
nuted ?sh ‘viscera in an aqueous suspension to
tract contains water soluble vitaminsiand other
the digestive action of pepsin at about pH 1.5
and at temperatures not substantially exceeding 35 water soluble digestion products of the entrails I ‘
including such constituents in the form '0! their
about 1009-1". for about two days, adding alkali
to adjust the pH to about 3, removing theliquid
acid salts.
from the solid undigested residue, separately re- . /
14. The process of ‘recovering both vitamin
containing oils and water-soluble vitamins irorn
covering vitamin-containing. oil and vitamin
cOntaining aqueous solution from the liquid,
' ‘
?sh viscerav which comprises'subjecting ?sh vis- '
cera-to the'digestive action of ‘pepsin under acid
heating the solid residue resulting from the re
moval of the liquid to aboutl37° C. and subject
ing the residue to a filtering operation to recover
conditions 'and subjecting the still acid digestion
product vto a separation treatment to remove vita
min-containing oil and an acid aqueous vitaminf
~ ‘
containing extract therefrom, which aqueous ex: p- ‘
6. A process of recovering vitamin-containing
tract contains water soluble vitamins and other
materials which comprises subjecting commie
water soluble digestion products of the entrails
nuted ?sh viscera in an aqueous suspension to
including such constituents in the form of their
the digestiveaction oi pepsin atla pH of‘ about
acid salts and’ said separation treatment includ
1.5, increasing the pH to about 3 after such diges?
tion, and subjectingthe still acid digestion prod 50 ing a ?ltration separation of oil from the 'warm
residue after the separation of the aqueous. solu- '
tion therefrom.
- not to a separation treatment to- separate vita
min-containing oiltherefrom.
15. vThe method or recovering vitamin-contain- ' "
7. A process of recovering‘vitamin-containing
ring materials fromi?sh viscera which comprises
nuted fish viscera‘. in an equeous'suspension to 55 subjecting comminuted ?sh'viscera in an aqueous
suspension to the digestive action 01 pepsin under
the digestive action of pepsin at a pH oi’ about
materials which comprises subjecting commi
, acid conditions and at a temperature below that
1.5, increasing the pH to about 3 after such diges
tion, and subjecting the still acid digestion prod
of substantial decomposition of the vitamins, re
moving the aqueous liquid-from the solid residue
60 and subjecting the solid residue. with admixed
‘ ' not to a‘separation treatment to separate vita
min-containing oil and an acid aqueous ~1- itamin
containingextract therefrom.
' oilto ?ltration after partial drying and at a tem
perature ‘at whch the oil is liquid‘ to facilitate
8.‘ A process of recovering both vitamin-com
' separation of oil from the solid residue. -
ing oils and waterv soluble vitamins from ?sh vis- .
16. A concentrated vitamin'B-containing prod
cera which comprises subjecting comminuted ?sh 85 uct resulting from the peptic digestion of ?sh
.viscera to the digestive action of pepsin at a pH
jvis'cera?under acid conditions, said product being" T ’
of about 1.5,and subjecting the resulting still acid
substantially free from oil and‘from waterinsolu
ble products of digestion and containing water
digestion product .to a~ separation treatment to
remove, vitamimconta'ining oii and a vitamin
containing aqueous solution.
. soluble vitamins of fishlviscera and .water soluble
9.. The process according to the preceding blaim_
inwhich the acid aqueous solution is subjected to
protein digestion productsof ?sh ‘viscera includ
ing such products in the form ofhydrochlorides.
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