Патент USA US2406249код для вставки
Patented A". 20, 1946 ' UNI-TED STATES PATENT ' orrljce ~ SALVAGE FROM FISH VISCERA ’ Ivan A. Partentiev, Nanuct, N. Y. No Drawing. Application November 25. 1943, ~ Serial No. 511,704 reclaims. 1 . 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. , k This application is a continuation-in-part of my application Serial No. 448,648 ?led June 26, 1942. . (cue-11) _ . ~ 2 . ‘ - 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. I 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 vitamins. 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 vitamins. . 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 ber 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 2,406,249 ' ,- and the same oil, stored in the white glass bot-r tles, without preservative, still had 7,584 I. U. of . 4 e?iciently. Furthermore, the muscle tissues'of 1 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‘ _ . Example 2 . . _ 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 16 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 v 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 1 Pantothenic acid ....... ..; ____________ -_ 186.2 -Nlcotinic acid _____ -'_.._'_ _______________ _'_ 41.3 gestion method agreed very closely with that ‘ found in oil obtained by extraction methods, thus 35 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 45 Nicotinic acid .... __- _________________ __ 2.4 Pantothenic acid _.._‘ _____ _._' _________ .._‘__ "1.12 Biotin _________ __.._'_ ________________ -- 0.063 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 _________________________ __ 31 ‘Pantothenic acid -__-__--..'_ _____________ __ 14 Biotin _ ' ‘ Example 3 _ v 0.8 . 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 5 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 preservatives. - - 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 The 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. 1 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 phate. 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. I‘clalm: ’ r 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. , . p 1 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, oil. ' ‘ ' " , " ?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 additional ' 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. I . soluble vitamins of fishlviscera and .water soluble ' 9.. The process according to the preceding blaim_ inwhich the acid aqueous solution is subjected to 70 protein digestion productsof ?sh ‘viscera includ ing such products in the form ofhydrochlorides. ‘ ' ~- , PARFEN‘I'JEV."