CA1078249A - Low carbohydrate oilseed lipid-protein comestible - Google Patents
Low carbohydrate oilseed lipid-protein comestibleInfo
- Publication number
- CA1078249A CA1078249A CA288,944A CA288944A CA1078249A CA 1078249 A CA1078249 A CA 1078249A CA 288944 A CA288944 A CA 288944A CA 1078249 A CA1078249 A CA 1078249A
- Authority
- CA
- Canada
- Prior art keywords
- protein
- oilseed
- retentate
- lipid
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J1/00—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
- A23J1/14—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from leguminous or other vegetable seeds; from press-cake or oil-bearing seeds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C11/00—Milk substitutes, e.g. coffee whitener compositions
- A23C11/02—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins
- A23C11/10—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins containing or not lactose but no other milk components as source of fats, carbohydrates or proteins
- A23C11/103—Milk substitutes, e.g. coffee whitener compositions containing at least one non-milk component as source of fats or proteins containing or not lactose but no other milk components as source of fats, carbohydrates or proteins containing only proteins from pulses, oilseeds or nuts, e.g. nut milk
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L11/00—Pulses, i.e. fruits of leguminous plants, for production of food; Products from legumes; Preparation or treatment thereof
- A23L11/60—Drinks from legumes, e.g. lupine drinks
- A23L11/65—Soy drinks
Abstract
LOW CARBOHYDRATE OILSEED LIPID-PROTEIN COMESTIBLE
Abstract of the Disclosure An oilseed lipid-protein product adapted for food use is prepared by aqueous extraction of fat containing oilseed materials including the ground raw oilseed or full-fat oilseed flour or flake at a pH in excess of the isoelectric range of the protein for the purpose of solubilizing the protein. Insoluble material is removed by centrifugation or filtration, and soluble carbohydrate is removed from the resulting lipid-protein emulsion by membrane filtration.
Abstract of the Disclosure An oilseed lipid-protein product adapted for food use is prepared by aqueous extraction of fat containing oilseed materials including the ground raw oilseed or full-fat oilseed flour or flake at a pH in excess of the isoelectric range of the protein for the purpose of solubilizing the protein. Insoluble material is removed by centrifugation or filtration, and soluble carbohydrate is removed from the resulting lipid-protein emulsion by membrane filtration.
Description
1~7824g LOW CARBOHYDRATE OILSEED LIPID-PROT~IN COMESTlBLE
Field of the Invention This invention is concerned with seed protein isolation and utilization. An oilseed fat containing protein product is produced.
Descri tion of the Prior Art P
The prior art has dealt extensively with the subject of isolation, purification and improvement of the nutritional quality and flavor of oilseed protein and particularly soybean protein for the purpose of adapting these plentiful and inexpensive proteins for human consumption. Soybean protein in its native state is unpalatable and has impaired nutritional quality due to the presence of antinutritional factors which interfere with mineral absorption and protein digestion. Other oilseed proteins suffer from s-lmilar disadvantages including the presence of toxic principles.
The prior art has dealt with the treatment and formulation of sources of these proteins in their native state such as the whole ,; ~ .
bean or seed and flours prepared therefrom to prepare palatable and digestible beverages, concentrates, or dried forms thereof which may be used to fortify other foods. The prior art has also dealt with the isolation and purification of these proteins for use as food ingredients.
The Pollowing patents deal with the preparation of whole bean oilseed lipid-protein beverages.
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C. P. Miles, "Process fQr Producing Milk from Soybeans", 'U. S. Patent No. 3,288,614, patented November 29, 1966. Soy milk is prepared by dry cracking and dehulling of the soybeans, and passage thereof through flaking rolls under heavy pressure; suspension of the soy flakes in water followed by the additi~n of a phosphate or sequestering agent stabilizer; pressure cookinK; homogenizing;
clarifying in a centrifugal separator and formulating with other ingredients to prepare a milk-like product.
A. I. Nelson, et al. "Soybean Beverage and Process", U. S. Patent No. 3,901,978 patented August 26, 1975. The process involvei soaking whole soybeans to tenderize them; boiling with dilute sodium bicarbonate solution to inactivate trypsin inhibi~or and the lipoxigenase enzymes; wet ~rinding; and homogenizing to form a bland stable aqueous dispersion of whole soybeans.
The following patents are concerned with the preparation of purlfied oilseed proteins for food use and involve membrane filtration of extracts containing the protein and carbohydrate constituents of the oilseed in solution. Each of these processes is distinguished ; from the foregoing in that defatted oilseed raw materials are employed and a fat free purified protein isolate is the end product.
Iacobucci, et al., U. S. 3,736,147 patented May 29, 1973 ~ disclose an ultrafiltration process for the preparation of soy protein ;! isolate having a reduced phytic acid content which involves various chemical treatments in combination with extensive ultrafiltration.
Chemical treatment involves either enzymatic hydrolysis of the phytic acid by the enzyme phytase at neutral pH prior to ultrafiltration, ultrafiltratlon in the presence of calcium ion at low pH, or the use of ethylenediatinetetr:~cetic acid at t high ~d.
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: " ~078249 Frazeur, et al., ~. S. 3,728,327 patented April 17, 1973 disclose a membrane separation process for preparation of a soy protein isolate which requires homogenization of a soybean slurry followed by centrifugation and extensive reverse osmosis or ultrafiltration of a highly dilute solution followed by spray drying of the retentate.
O'Connor, U. S. 3,622,556 patented November 23, 1971 is concerned with the preparation of a sunflower meal protein isolate which involves removing green color forming precursors from the protein by ultrafiltration.
One of the chie$ disadvantages of the liquid soy lipid-protein products produced by the Miles or Nelson, et al.
methods is that the soluble soybean carbohydrates are retained in the end product. These carbohydrates are not fully digestible by human beings and are responsible for flatulence and other lS digestive disturbances following consumption thereof. The prior art has not addressed the possibility of adapting the membrane filtration techniques represented in the Iacobucci, et al., Frazeur, et al., and O'Connor patents to the elimination of soluble carbohydrates from the liquid soy lipid-protein products of the sort illustrated in the other patents cited.
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~ Summary of the Invention ,, ' The invention concerns a membrane filtration process for the elimination of soluble carbohydrate from an aqueous oilseed lipid-containing suspension or emulsion containing dissolved and/or suspended protein, and dissolved carbohydrate. The emulsion is ' ~
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prepared by aqueous extraction o~ a ~at-containing particulate ,oilseed raw material at a pH in excess o~ the isoelectric range of the oilseed protein. The ground whole bean or seed may be employed or a fat-containing flour prepared from the oilseed is suitable. Mixtures of full fat and defatted flours may be used.
The emulsion after removal of particulate material by filtration or centrifugation is purified by membrane filtration.
Thus broadly, the invention contemplates a process for preparing an oilseed lipid-protein comestible which comprises forming an aqueous suspension of edible oilseed containing suspendeld oilseed lipid, dissolved ollseed protein, and dissolved oilseed carbohydrate at a pH in excess of the isoelectric range of the protein, with the suspension being obtained by aqueous extraction of particulate oilseed material containing lipid, protein, and carbohydrate at a pH in excess of the isoelectric range of the .j protein, separating particulate material from the suspension to yield an emulsion containing suspended lipid, dissolved protein, and dissolved carbohydrate, and separating carbohydrate from the emulsion by filtration employing a semi-permeable membrane which has the capability to retain suspended lipid and dissolved protein as retentate, and to pass dissolved carbohydrate as permeate.
The invention also contemplates and includes the novel ; products of the inventi-ve process.
In one preferred form of the process, extraction of the oilseed material at a pH in excess of pH 10.1 and preferably pH 11-12 followed by centrifugation results in substantial elimina-tion of phytic acid components from the resulting product. In a : .
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further preferred form, high-temperatllre short-time heat trea~ment is applied to the emulsion-contalning suspended lipid materlals either prior to or after membrane filtration which results in an lmprovement in the nutritional quality and functionality with respect to shelf stabllity and physical characteristics of products formulated from the novel product.
Oilseeds useful in the invention include chickpea, rapeseed, -~-coconut, cottonseed, peanut, safflower seed, sesame seed, soybean, and sunflower seed. Soybean is considered representative of these 10 oilseeds and i5 used for the purpose of illustration in this disclosure.
Other seeds containing substantial amounts of protein and oil can be treated in a manner similar to that described below with modifications whlch will be within the knowledge of those skilled in the art. Soy-bean is the preferred oilseed for application of the present invention.
15 Detailed Description of the Invention Raw ~laterials and Pretreatment.- Ground whole soybeans are r the preferred starting material for the present invention. Ground dehulled beans may be employed, but there i9 no advantage since lnsoluble material and soluble carbohydrates are removed at 20 later stages of the process and the presence of the hulls does not burden these removal steps. Grinding may be accomplished in the dry state or ~et grinding of a water suspension of the beans may be employed. It ls preferred to employ temperatures in excess of about 10C. in the interest of secur~ng the optimal protein quality 25 and extraction yields with efficient phytate removal when the latter i8 sought. Excessive heating of the particulate soybean material -~078Z49 prior to extraction appcars to rcduce the solubillty o the protein and form an alkali-stable bond betwee~ the phytate components and other alkali-soluble soybean constltuents, probably protelns, whlch reduces the efficiency of phytate removal as is described below.
If desired, th~ beans may be blanched prior to ~rlnding but, if thls ls done, the heating per~od should be limited and blanching should be conducted in such a way as to avoid a decrease in protein yield. Similarly, commercial full fat soy flour may be employed as raw material, but again it is preferred to select a flour which has not been heated slnce this reduces the efficiency of protein extr~ction and phytate removal as has been mentioned. Mlxtures of fat-containing and defatted flours may be used. Blanching of the whole bean and wet grinding is believed to improve the or~anoleptic qualities of .. . .
; the product resulting from the present invention.
When a low phytate product is desired as is the case according to a preferred embodiment of the invention, the particulate soybean raw material should not have been previously treated with acld. Contact of the native soybean protein with acid in the presence of the phytic acid constituents of the bean results in the formation of an alkali-stable bond which reduces the efficiency of the method described below for elimination of the phytic acid constituents. Accordingly, particulate soybean materials such as acid precipitated soybean concentrates which are prepared by extraction of soluble carbohydrates from soybean material with acid at the lsoelectric value of the soy protein are not suitable tartlng =ater~a-a.
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Step (a~ Formatlon of ~n ~queous Suspcnsion o~ Sovbean Lipid.- The suspension is formed at a pl~ in exccss of the iso-electric value of the soy protein cmploying one of the lipld containin~ particulate soybean materials referred to above.
The particular pH selected for this stage of the process depends on the type of product being sought. From the standpoint of main-taining maximum protein quality, pH 7-9 is preferred and, in any event, a pH of less than 10. Within this P~ range of from the isoelectrlc value to pH 10, the phytic acid constituents are soluble and are carried through the process with the protein. If i~ is , desired to eliminate the phytic acid constituents, the suspension ~ ln step (a) is formed at a p~ of pH 10.1 to pH 14 w$thin which ,~ range the phytates are rendered insoluble and are separated with other insoluble constituents in a subsequent step.
Ordinarily, from 4 to 40 parts by weight of water or aqueous alkaline solutlon per part by weight of particulate soybean material ;~ ls employed for extraction. Preferably from 8 to 16 parts by weight of water or aqueous solution are employed. Sodium hydroxide, potassium hydroxide, or other nontoxic water soluble base which is suitable for food use and which is compatible with the soy protein may be used for basification. Alkaline earth metal hydroxides such as barium hydroxide or calcium hydroxide under some conditions of use cause precipitation of the soy protein and are not preferred.
If the ob~ective i5 to secure maximum recovery of protein in the extract, relatively large amounts of extract water or alkaline ; solution are employed and the solids may be removed by centrifu-gation and re-extracted. I~here residual olids are to be used ~ 7 ~
, ., for anlmal feed, it may be dcslrable to conduct a less thorough extractlon or to omi~ washing of the solids after removal of the supernatant liquld. Similarly, times and tempcraturcs are varied to suit the particular operating purposes and equipment, but lt is preferred to limit the exposure at hlghly alkaline pH values such as pH 12 or more to no more than 25C. for 2 hrs in order to avoid chemical degradation of the protein.
Where it is desired to eliminate the phytic acid con-6tituents and obtain a soybean lipid protein product which is low in both carbohydrate and phytic acid components, the suspension 6hould be formed in step (a) at a pH in the range of 10.1 to 14, preferably pH 11-12, and more preferably pH 11.4-11.8. This results in disruption of the soluble phytic acid soy protein association and insolubilizes the phytates. When the terms phytate or phytates are used herein, it is intended to include salts of phytic acid or molecular complexes of phytic acid with other soybean consti~uents. After the phytates are rendered insoluble st pH 10.1-14, the phytates are separated by conventional solid separation techniques such as centrifugation or filtration in a subsequent step of the process.
As to the alkaline treatment in step (a), it has been found that the phytate content of the extract drops abruptly at pH's in excess of pH 10.1. At pH 10.6 an extract is produced having a phytate content of about 1 g./100 g. of so~ids in the extract.
25 At pH 11.0 the phytate content of the extract is about 0.05 g./100 g.
of sollds in the extract. When reference is made herein to a "low phytate" product, what is intended is one having less than 0.5 g.
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phytate per 100 g. of solids, and preferably less than 0.3 ~. phytate per 100 g. of solids. As the pll is increased, the tendency to hydrolyze the protein and effect condensation through the sulfur contai~ing amino acids increases. While phytate removal takes place at all pH values in excess of pH 10.1, it is more efficient at pH values in excess of p~ 11Ø It is preferred to operate ln the range of about pl~ 12, and more preferably at p~l 11.4-11.8 to avoid as much as possible a loss in protein quality due to hydrolysis or condensation of sulfur-contalning amino acids, and still effect efficient removal of phytate. O
! The temperature during phytate separation following alkaline treatment should preferably be at lea~t 10C., for instance 10C. to 50C. or 15C. to 30C. It has been found that removal of phytate is incomplete but, nevertheless, significant at 10C. or lo~er following alkaline treatment at pH 11-12. At 10C. approximately one-half of the phytate is removed, while at 20C. 90% of the phytate is removed, and at 30C. more than 99% removal is effected. The foregoing temperature ranges are the optimum values for dissociation of the soluble soy protein phytic acid complex and for rendering of the phytates and phytic acid derivatives insoluble. Under some manu-facturing conditions, however, other temperature ranges may prove to be more suitable since the temperature at which the phytate precipitate is formed has an effect on the physical nature thereof which affects its filtration and centrifugation characteristics.
Empirical selection of the optimum phytate insolubilization tempera-ture for any given manufacturing arrangement is desirable. Optimum values usually fall within the range of 15C. to 30C. At tempera-tures in excess of 50C. the tendency for hydrolysis of the pFotein, :' ' -1~78Z49 and for the formatlon of undesirable proteln rcaction products increa~ses, the higher tcmperatures are thus to be avoided.
The time of exposure of the soy protein containing extract to aqueous base ~n the range of p~l 10.6-14 durlng phytate precipitation S should be limited according to the temperature employed so that substantial loss in protein quality does not occur. A convenient way to ascertain this is to determine the cysteine content of the protein since cyqteine is the most sensitive of the amino acids to loss from the soy protein under the alkaline conditions employed.
It has been found that at pU 11 and at temperatures in the range of 20-30C. eæsentially no loss of cysteine occurs during periods of up to 6-3/4 hours. However, at pH 12, significant loss of cysteine i occurs within 2-3/4 hours at 40C. At 20C. and pH 12 the loss of cysteine is not believed ~o be significant during 2-3/4 hours, but after 6-3/4 hours, approximately 15% of the cysteine is lost.
Accordingly, a period of up to about 1/2 hour for phytate precipi-tstion is recommended, but longer periods are satisfactory when operating at the lower end of the pH range of about pH 11. At pH values of 12 and higher careful limitation of the time of exposure to the alkaline medium should be exercised by moni~oring the content of the amino acid cysteine.
In summary, the duration of exposure of the alkaline aqueous ex~ract of soybean material in the range of pH 10.6-14 for the purpose of phytate precipitation should be chosen so that under the conditions of pH and temperature employed the duration of exposure is such that not more than about 10% of the cysteine of the 50y protein containing extract is destroyed. Treatment conditions resulting in substantially .~ .
`` 249 more cystelne destructlon than 10% are regarded as inapproprlate since one of the ob~ects of the present invention i9 to provide a soy protein of lmproved nutritional quality whlch purpose ls defeated by degradation of the soy proteln and loss of certain amino acid values, particularly cysteine.
Step (b) SeParatiOn of Particulate Material.- Step (b) involves separation of the spent fla~es and of the insolubili~ed `phytate when the process i9 operated in such a manner as to insolu-bilize phytate from the extract. There is obtained an aqueous emulslon of susper,ded lipid materlal whlch may contain suspen~e~
protein, as well as dissolved protein, and dissolved carbohydrate.
Conventional solld separation unit processes may be employed such as centrifugation. The same constraints on time, temperature and pH which are applicsble durlng formation of the extract in step (a) are applicable during separation of the particulate material in step (b).
The aqueous emulsion of soybean lipld from which partlculate material has been removed is most convenient for further processing if it contains from 1-12% by weight of protein, 1-10% by weight of carbohydrate and associated mineral constituents which are dlssolved during the extraction process. If extracts are prepared containing more than 12% by weight of protein, they are ~enerally viscous and both inconvenient to handle and inefficiently procèssed in the centrifugation or filtration and washing steps.
In one preferred mode of operation, the emulsion produced in step (b) is sub~ected to high-temperature short-time heat treatment at a pH of less than pH 10 but greater than the isoelectrlc value of , . .
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the soy proteln, for ins~ance pll 6-10, and preferably pH 7Ø A
tempera~u~'e in thc range of from 60C. to 150C. for a period of from 1 sec. to 30 mln. is employed. The selection of the proper combination of time ~nd temperat:ure is discussed in more detall ~ 5 below. Ileat treatmen~ at this Rtage has the bencfit ol lncreasing ; the ultrafiltration ~lux rate ln step (c) an-l o reducing the mlcrobial population sufficiently ~o eliminate spoilage durlng the ultrafiltration fitep.
SteP ~ _hydrate Separation.- Filtration in step (c) 10 ig prlferably carrie~ out usin~ a so-called ultrafiltration apparaLus containing a semi-permeable membr~ne which wlll retain protein con-; stituents, and allow dissolved lower molecular wcight materlals to pass.
Seml-permeable membranes having the capability of retaining protelns having a minimum molecular weight in the range of abou~ 10,000-; lS 50,000 daltons are useful. The apparatus is operated at a gauge press~re of about 25 psig but pressures in the range of about 15 to 100 psls and hlgher are useful. Ultraflltra~ion according to the pre--sent inventlon is to be distinguiYhed from o~her membrane filtration proccsses in respect o~ the porosity of the mar.~brane employet 20 ant the pressure m~intained on the retentate to force passage of exces~ water and low molecular weight ingredients. Reverse "' 08mo6is processes, for example, use membranes having much lower porosity and retain much lower molecular weight materials such ~' ' 88 the carbohydrate constltuen1-s of the soybean which it is ,, desired to eliminate by the present process. Reversc osmosis ; processes are also considerably more. expensive to operate in ~ that hi~her operatin~ pressures and generally lower flux rates 7 ~re involved.
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~078249 We have made the surprising dlscoveries that the prescnce of suspended or emulslficd fat in the extract from whlch the carbo-hydrates are to be removed by ultrafiltration does not interfere with the efficiency of the ultrafiltration and that the suspended or S emulsified fat remains in the retentate. Thus, it is possible to prepare a highly desirable nutritional product containing both fat and protein and little carbohydrate. The carbohydrates have long been known to be amonR the undesirable constituents of the soybean from the standpoint of human consumption.
Filtration employing a semi-permeable membrane is ~referably carried out at a pH in the range of pH 6.5 to pH 7.5 for the purpose of maintaining protein inte~rity but this is not essential. At pH values in excess of pH lO some filtration membranes may be subject to deterioration or damage and, furthermore, a loss in protein quality is more likely to occur. Therefore, it is preferred to conduct the membrane filtration step at a pH in the range of about pH 6-10, more preferred at pH 6.5 to pH 7.5, and, ln any event, at a pH in excess of the isoelectric range of the protein.
The suspension which is subjected to ultrafiltration and the retentate during the ultrafiltration process is preferably malntained a~ a temperature in the range of about 45C. to 75C.
to improve the flux rate and to minimize bacterial spoilage.
With respect to the latter point, a temperature of at least about 25 60-65C. is preferredO Temperatures in excess of 75C. are undesirable since chemical decomposltion and condensation reactions of the protein occur with the formation of undesirable byproducts - .
1(~78249 and loss in protein quallty. Below about 60C. pasteurization is less effective and spoilage may occur. Below about 45C. the benefit to flux rate lmprovement diminishes.
~ It is preferred to produce a final liquid soy lipid-protein comestible having a protein concentration of about 3% to 7% by weight, but for some purposes lower or higher concentrations may be desirable.
The proteln concentratlon of the soy protein can be readily ad~usted to any value in the range of 1% to 12% by weight by appropriate manlpulation of volumes of extraction water, permeate collected, or evaporative concentration or dilution may be employed as long9as the protein remains in solution. Protein solutions having concentrations of less than 1% by wei~ht are uneconomical and of little practical lnterest. For instance, when commencing with a particle-free emulsion having a protein concentration of 3.5~, removal of half of the volume as permeate results ln a retentate having a protein ; concentratlon of 7%. ~ substantial reduction in carbohydrate and mineral content occurs through elimination of these ingredients wlth the permeate water. Since the soybean carbohydrate substituents are generally undesirable nutritional ingredients due to their dlfficulty of digestion by man, lt ls desirable to eliminate a ma~or proportion thereoi.
We have expressed the carbohydrate content of the soybean lip$d-protein comestibles prepared ln our present studies as protein coefficient which is the ratio of the protein content thereof to the total of the protein and carbohydrate content. For infant formula use we prefer a protein coefficient of about 0.90 or more since the soyb=an carbohydrates ~ause flatulents and undes1rab1e stoo1s ~078Z49 ln infants subsisting on the soy proteln based formula. ~queous llpld-protein comestibles havin~ proteln coefflcients of about 0.8 are suitable for the fortification of conventional foods 8uch as meat and bread and for the preparation of liquld dietary products for more mature sub~ects.
It has been found tlat by concentration of a 3.5~ by weight protein containing extract by ultrafiltration to one-half of its original volume that the retentate still contains an undesirably high proportion of carbohydrate for infant formula use. Such product is suitable for certain other food uses, however. I~e O
have found that diafiltration (a form of ultrafiltration in which the retentate i6 continuously diluted with water or a wash solution) is an appropriate way of eliminating additlonal undesired carbo-hydrate and mineral constituents. This amounts simply to continuously adding a diafiltration solution, preferably water, to the retentate as it is circulated through the filtration apparatus and permeate is removed. Diafiltration thus constitutes a washing operation in whlch the undeslred low molecular weight constituents are washed from the retentate.
Referring to the original volume of particulate-free emulslon as one ln a preferred form of the process, ~ volume of permeate is removed by ultrafiltration and then from ~ to 2'~
volumes of water are used for dilution of the retentate during diafiltration until the total permeate collected i9 Up to 3 volumes.
Dilafiltration to provide a larger permeate volume affords little additional purification. Diafiltration may be commenced at a gradual rate near the beginning of the ultrafiltration, and the .' ~ ' . ' ' rate increased as the desired protein concentration is approached, or alternatively, concentratlon to the desired protein content may precede diafiltration.
Instead o water, diafiltration solutions containing desired ingredients for the final product, or which improve protein retention or flux rate may be employed. In the case of lnfant formula products, additional ingredients of the flnal formulated product which contain ~he present soy protein solution as a principle protein ingredient which may be combined therewith ~ 10 during the diafiltration stage include carbohydrate, fat, ando ; mineral constituents. While this may offer an advantage in some instances, it is generally not a preferred mode of operation since at least a portion of these additives will be lost to the permeate by passage through the membrane. These losses can in part be offset by recovery of the desired ingredients from the permeate or by recycling the permeate to the diafiltration water.
A desirable ad~unct to the process constituting an additional novel feature of the invention involves high-temperature short-time (HTST) heat treatment of the extract, and/or retentate, and/or of a liquid dietary product formed from the latter. This - modification, constituting a preferred version of the present invention, has several purposes. When conducted prior to ultra-filtration, heat treatment has the benefit of reducing the bacterial ^ count and minimizing the risk of spoilage of the clarified extract during further processing including ultrafiltration. It has the further benefit of facilitating the ultrafiltration step since it has been found that the flux rate at which permeate is formed during ,~
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1~78Z4g ultrafiltration is increased when the partlculate-free emulsion ls beated prior to ultrafiltration. High-temperaturc short-time heat treatment whcn used in conJunction with ultrafiltration to produce a lipid-protein comestible is considered part of the S present invention as are the protein isolates produced thereby.
The latter may be formulated as is with the protein in the dissolved state, or they may be dried.
From the standpoint of the utility of the aqueous lipid-protein comestib~e of the present invention in forming liquid : 10 dietary products such as infant formulas, milk substitutes, an,dmeal replacements or supplements, heat treatment has the benefit of improving the nutritional quality of the protein, and of improving the functlonality of the protein including a reduction of the viscosity of solutions thereof, and improvement in solubility 15 and fat emulsification properties. These benefits are derived ' whether heat treatment takes place before or after ultrafiltration.
The time and temperature conditions which are operable for the foregoing purposes do not lend themselves to precise definition, but those skilled in the milk treatment and soy protein g 20 extraction arts will have no difficulty in selecting optimum conditions for the particular manufacturing facilities which are ; availsble. Broadly speaking, the higher the temperature employed, the shorter tbe time of treatment with the maximum temperature presently considered applicable being about 150C. for a period 25 of 1 sec. ~h`en lower temperatures are employed, longer time periods of treatment are necessary, for instance 60C. for about 30 min.
has substantially equivalent effect to 150C. for 1 sec. Other : ~:
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, 1~78249 suitable times and temperatures including 130C. for 45-60 secs.
and 100C. for 10 min.
In one preferred mode of the short-term high-temperature ; heat treatment modificatlon of the process, the heat treatment step S is divided so that a relatively mild heat treatment is employed prior to ultrafiltration for the purpose of reducing spoilage and improving flux rate, and then a more severe heat treatment i9 employed on the finlshed soy protein retentate after removal of the carbohydrate constituents. This has the advantage of minimiYing the brownlng reaction which results from an interaetion of the soybean carbohydrate with the soy protein which has a tendency to occur when carbohydrate containing soy protein extracts ; are heated. For example, the clarified extract Just prior to ultra-filtration may be given a mild heat treatment of from about 60C. for 15 30 min. to 130C. for l min., cooled to a temperature of about 45-75C.
and then purified by ultrafiltration as is described above. The ~, resulting aqueous purified soy protein solution retentate may be then given a further more severe heat treatment for the purpose of improving the functionality of the protein and destroying anti-nutritional factors. For this second heat treatment, a temperature in the range of about 110C. for 1 min. up to about 150C. for 1 sec.
may be employed. The second heat treatment may be incorporated with subsequent process steps whereby a liquid dietary product is produced i from the aqueous purified soy protein by combining other ingredients:' therewith.
The preferred heat treatment conditions for a given appli-cation of the process are determined empirically and adapted to the :~
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--^-~078249 avallable equlpment by evaluatlng ~he performance of the heated extract when heatlng is carried out for dif~erent time periods and at different temperatures. For some purposes, one set of heat treatment conditions may be preferred while another set may be 5 preferable when the resulting aqueous purified soy protein ~ ;
solution is to be used for a different purpose. In any event, the conditions are selected to achieve one or more of the following results:
(i) improving the protein efficiency ratio of said lipid-protein comestible produced in step ~c), or of a liquid dietary product prepared therefrom;
(ii) improving the functionality of said lipid-protein comestible produced in step (c) or of a liquid dietary product prepared therefrom as measured by sedimentation :~.
lndex, ni~rogen solubility index, or emulsion stability index, (iii) increasing the ultrafiltration flux rate in step (c), or (iv) reducing the microbial population of said particulate free emulsion and said retentate sufficiently to substantially eliminate spoilage thereof during ultrafiltration in step (c).
For food applications, the liquid lipid-protein comestible produced as retentate according to the process described above may be dried by conventional methods including freeze-drying and spray-drying, and the dry powder used as a food ingredient. For the preparation of beverages such as soy milks, the retentate without .,:
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~78Z49 drying is preferably comblned with other desired ingredients such as carbohydrates, fats, vitamins, minerals, etc. and the coml)osition homo~en~zed and, if desired, canned and sterilized. The food products and bevcrages have improved nutritional value, stabllity, and functional qualities.
Description of Specific Embodiments ExamPle 1.- Seed grade soybeans were ground twice in a hammermill employing a very slow feed rate to prevent the development of excessive heat to provide a coarse flour. The tempreature of the flour at the end of each grinding period was 44C. A suspension of 250 g. of the ground beans in 4 1. of deionized water at room temperature was prepared in a vessel equipped for mechanical agitation and the pH of the suspension was adjusted to pH 9.0 by addition of 10% aqueous sodium hydroxide. The suspension was thoroughly mixed at this pH and at room temperature for 30 min. and the insoluble material was then separated by centrifugation at 4022 x G. The supe matant liquid was again transferred to the vessel equipped with the agitator and adjusted to pH 11.6 wlth 10% aqueous sodium hydroxide and mixing at room temperature was continued for another 30 min. period. ~ -20 The suspension was then centrifuged at 13,218 x G and the supernatant liquid comprising an emulsion of the soybean lipid-protein in a solution of soy protein and soy carbohydrate was subjected to ultrafiltration at 46C. and 40 psi. employing a semi-permeable membrane capable of retaining proteins having molecular weights ; 25 in excess of 30,000 daltons. The emulsion was concentrated by ultra-; filtration to one-half of its original volume~ and then further .
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purified by diafiltration involving dilution of the concentrated retentate wlth deioni~ed wa~er at the same raee that permeate was being collected so as to maintain the volume of the retentate constant.
A volume of diafiltration water equal to the orlginal volume of the emulsion charged to the ultrafiltration apparatus was employed. The retentate was then freeze dricd and analyzed. The results obtained are given in the following table along with the results of four other examples conducted in similar fashion but employing either different pH values and times for extraction or employing commercial full 1~ fat soy flour as raw material rather than ground whole soybean.
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1078;~49 The protein coefflcient is a measurc of the rclatlve removal of carbohydrate and retention of protein by the membrane filtratlon step. The protcln cocfficlent ls the ratlo of the proteln content on a welght basis of the product to the sum of the protein content and carbohydrate content on a welght basis.
Protein was determined by the method of Lowry, et al., Journal of Biological Chemistry, 193:265-275 (1951) and carbohydrate was determ~ned by the method of Dubols, et al., Analytlcal Chemlstry 28:350-356 (1956). Phytic acid was determlned by the method of 10 Wheeler, et al., Cereal Chemistry 48:312-320 (1971).
It is evident by comparison of the phytic acid composltion of the products of Examples 1 and 2 wlth that of Example 3 that extraction at pH 11.6 results in substantlal reductlon or virtual ellmination of phytic acid from the product. Phytlc acld removal was unsuccessful in Example #5 and the protein yields in Examples 4 and 5 were both substantially lower than in Examples 1-3. Carbo-hydrate removal was good ln all instances, however. Examples 4 and 5 employed commercial full fat soy flour as raw materlal whlch had been toasted by the manufacturer at about 65C. for 20-30 min.
Field of the Invention This invention is concerned with seed protein isolation and utilization. An oilseed fat containing protein product is produced.
Descri tion of the Prior Art P
The prior art has dealt extensively with the subject of isolation, purification and improvement of the nutritional quality and flavor of oilseed protein and particularly soybean protein for the purpose of adapting these plentiful and inexpensive proteins for human consumption. Soybean protein in its native state is unpalatable and has impaired nutritional quality due to the presence of antinutritional factors which interfere with mineral absorption and protein digestion. Other oilseed proteins suffer from s-lmilar disadvantages including the presence of toxic principles.
The prior art has dealt with the treatment and formulation of sources of these proteins in their native state such as the whole ,; ~ .
bean or seed and flours prepared therefrom to prepare palatable and digestible beverages, concentrates, or dried forms thereof which may be used to fortify other foods. The prior art has also dealt with the isolation and purification of these proteins for use as food ingredients.
The Pollowing patents deal with the preparation of whole bean oilseed lipid-protein beverages.
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C. P. Miles, "Process fQr Producing Milk from Soybeans", 'U. S. Patent No. 3,288,614, patented November 29, 1966. Soy milk is prepared by dry cracking and dehulling of the soybeans, and passage thereof through flaking rolls under heavy pressure; suspension of the soy flakes in water followed by the additi~n of a phosphate or sequestering agent stabilizer; pressure cookinK; homogenizing;
clarifying in a centrifugal separator and formulating with other ingredients to prepare a milk-like product.
A. I. Nelson, et al. "Soybean Beverage and Process", U. S. Patent No. 3,901,978 patented August 26, 1975. The process involvei soaking whole soybeans to tenderize them; boiling with dilute sodium bicarbonate solution to inactivate trypsin inhibi~or and the lipoxigenase enzymes; wet ~rinding; and homogenizing to form a bland stable aqueous dispersion of whole soybeans.
The following patents are concerned with the preparation of purlfied oilseed proteins for food use and involve membrane filtration of extracts containing the protein and carbohydrate constituents of the oilseed in solution. Each of these processes is distinguished ; from the foregoing in that defatted oilseed raw materials are employed and a fat free purified protein isolate is the end product.
Iacobucci, et al., U. S. 3,736,147 patented May 29, 1973 ~ disclose an ultrafiltration process for the preparation of soy protein ;! isolate having a reduced phytic acid content which involves various chemical treatments in combination with extensive ultrafiltration.
Chemical treatment involves either enzymatic hydrolysis of the phytic acid by the enzyme phytase at neutral pH prior to ultrafiltration, ultrafiltratlon in the presence of calcium ion at low pH, or the use of ethylenediatinetetr:~cetic acid at t high ~d.
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: " ~078249 Frazeur, et al., ~. S. 3,728,327 patented April 17, 1973 disclose a membrane separation process for preparation of a soy protein isolate which requires homogenization of a soybean slurry followed by centrifugation and extensive reverse osmosis or ultrafiltration of a highly dilute solution followed by spray drying of the retentate.
O'Connor, U. S. 3,622,556 patented November 23, 1971 is concerned with the preparation of a sunflower meal protein isolate which involves removing green color forming precursors from the protein by ultrafiltration.
One of the chie$ disadvantages of the liquid soy lipid-protein products produced by the Miles or Nelson, et al.
methods is that the soluble soybean carbohydrates are retained in the end product. These carbohydrates are not fully digestible by human beings and are responsible for flatulence and other lS digestive disturbances following consumption thereof. The prior art has not addressed the possibility of adapting the membrane filtration techniques represented in the Iacobucci, et al., Frazeur, et al., and O'Connor patents to the elimination of soluble carbohydrates from the liquid soy lipid-protein products of the sort illustrated in the other patents cited.
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~ Summary of the Invention ,, ' The invention concerns a membrane filtration process for the elimination of soluble carbohydrate from an aqueous oilseed lipid-containing suspension or emulsion containing dissolved and/or suspended protein, and dissolved carbohydrate. The emulsion is ' ~
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prepared by aqueous extraction o~ a ~at-containing particulate ,oilseed raw material at a pH in excess o~ the isoelectric range of the oilseed protein. The ground whole bean or seed may be employed or a fat-containing flour prepared from the oilseed is suitable. Mixtures of full fat and defatted flours may be used.
The emulsion after removal of particulate material by filtration or centrifugation is purified by membrane filtration.
Thus broadly, the invention contemplates a process for preparing an oilseed lipid-protein comestible which comprises forming an aqueous suspension of edible oilseed containing suspendeld oilseed lipid, dissolved ollseed protein, and dissolved oilseed carbohydrate at a pH in excess of the isoelectric range of the protein, with the suspension being obtained by aqueous extraction of particulate oilseed material containing lipid, protein, and carbohydrate at a pH in excess of the isoelectric range of the .j protein, separating particulate material from the suspension to yield an emulsion containing suspended lipid, dissolved protein, and dissolved carbohydrate, and separating carbohydrate from the emulsion by filtration employing a semi-permeable membrane which has the capability to retain suspended lipid and dissolved protein as retentate, and to pass dissolved carbohydrate as permeate.
The invention also contemplates and includes the novel ; products of the inventi-ve process.
In one preferred form of the process, extraction of the oilseed material at a pH in excess of pH 10.1 and preferably pH 11-12 followed by centrifugation results in substantial elimina-tion of phytic acid components from the resulting product. In a : .
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further preferred form, high-temperatllre short-time heat trea~ment is applied to the emulsion-contalning suspended lipid materlals either prior to or after membrane filtration which results in an lmprovement in the nutritional quality and functionality with respect to shelf stabllity and physical characteristics of products formulated from the novel product.
Oilseeds useful in the invention include chickpea, rapeseed, -~-coconut, cottonseed, peanut, safflower seed, sesame seed, soybean, and sunflower seed. Soybean is considered representative of these 10 oilseeds and i5 used for the purpose of illustration in this disclosure.
Other seeds containing substantial amounts of protein and oil can be treated in a manner similar to that described below with modifications whlch will be within the knowledge of those skilled in the art. Soy-bean is the preferred oilseed for application of the present invention.
15 Detailed Description of the Invention Raw ~laterials and Pretreatment.- Ground whole soybeans are r the preferred starting material for the present invention. Ground dehulled beans may be employed, but there i9 no advantage since lnsoluble material and soluble carbohydrates are removed at 20 later stages of the process and the presence of the hulls does not burden these removal steps. Grinding may be accomplished in the dry state or ~et grinding of a water suspension of the beans may be employed. It ls preferred to employ temperatures in excess of about 10C. in the interest of secur~ng the optimal protein quality 25 and extraction yields with efficient phytate removal when the latter i8 sought. Excessive heating of the particulate soybean material -~078Z49 prior to extraction appcars to rcduce the solubillty o the protein and form an alkali-stable bond betwee~ the phytate components and other alkali-soluble soybean constltuents, probably protelns, whlch reduces the efficiency of phytate removal as is described below.
If desired, th~ beans may be blanched prior to ~rlnding but, if thls ls done, the heating per~od should be limited and blanching should be conducted in such a way as to avoid a decrease in protein yield. Similarly, commercial full fat soy flour may be employed as raw material, but again it is preferred to select a flour which has not been heated slnce this reduces the efficiency of protein extr~ction and phytate removal as has been mentioned. Mlxtures of fat-containing and defatted flours may be used. Blanching of the whole bean and wet grinding is believed to improve the or~anoleptic qualities of .. . .
; the product resulting from the present invention.
When a low phytate product is desired as is the case according to a preferred embodiment of the invention, the particulate soybean raw material should not have been previously treated with acld. Contact of the native soybean protein with acid in the presence of the phytic acid constituents of the bean results in the formation of an alkali-stable bond which reduces the efficiency of the method described below for elimination of the phytic acid constituents. Accordingly, particulate soybean materials such as acid precipitated soybean concentrates which are prepared by extraction of soluble carbohydrates from soybean material with acid at the lsoelectric value of the soy protein are not suitable tartlng =ater~a-a.
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Step (a~ Formatlon of ~n ~queous Suspcnsion o~ Sovbean Lipid.- The suspension is formed at a pl~ in exccss of the iso-electric value of the soy protein cmploying one of the lipld containin~ particulate soybean materials referred to above.
The particular pH selected for this stage of the process depends on the type of product being sought. From the standpoint of main-taining maximum protein quality, pH 7-9 is preferred and, in any event, a pH of less than 10. Within this P~ range of from the isoelectrlc value to pH 10, the phytic acid constituents are soluble and are carried through the process with the protein. If i~ is , desired to eliminate the phytic acid constituents, the suspension ~ ln step (a) is formed at a p~ of pH 10.1 to pH 14 w$thin which ,~ range the phytates are rendered insoluble and are separated with other insoluble constituents in a subsequent step.
Ordinarily, from 4 to 40 parts by weight of water or aqueous alkaline solutlon per part by weight of particulate soybean material ;~ ls employed for extraction. Preferably from 8 to 16 parts by weight of water or aqueous solution are employed. Sodium hydroxide, potassium hydroxide, or other nontoxic water soluble base which is suitable for food use and which is compatible with the soy protein may be used for basification. Alkaline earth metal hydroxides such as barium hydroxide or calcium hydroxide under some conditions of use cause precipitation of the soy protein and are not preferred.
If the ob~ective i5 to secure maximum recovery of protein in the extract, relatively large amounts of extract water or alkaline ; solution are employed and the solids may be removed by centrifu-gation and re-extracted. I~here residual olids are to be used ~ 7 ~
, ., for anlmal feed, it may be dcslrable to conduct a less thorough extractlon or to omi~ washing of the solids after removal of the supernatant liquld. Similarly, times and tempcraturcs are varied to suit the particular operating purposes and equipment, but lt is preferred to limit the exposure at hlghly alkaline pH values such as pH 12 or more to no more than 25C. for 2 hrs in order to avoid chemical degradation of the protein.
Where it is desired to eliminate the phytic acid con-6tituents and obtain a soybean lipid protein product which is low in both carbohydrate and phytic acid components, the suspension 6hould be formed in step (a) at a pH in the range of 10.1 to 14, preferably pH 11-12, and more preferably pH 11.4-11.8. This results in disruption of the soluble phytic acid soy protein association and insolubilizes the phytates. When the terms phytate or phytates are used herein, it is intended to include salts of phytic acid or molecular complexes of phytic acid with other soybean consti~uents. After the phytates are rendered insoluble st pH 10.1-14, the phytates are separated by conventional solid separation techniques such as centrifugation or filtration in a subsequent step of the process.
As to the alkaline treatment in step (a), it has been found that the phytate content of the extract drops abruptly at pH's in excess of pH 10.1. At pH 10.6 an extract is produced having a phytate content of about 1 g./100 g. of so~ids in the extract.
25 At pH 11.0 the phytate content of the extract is about 0.05 g./100 g.
of sollds in the extract. When reference is made herein to a "low phytate" product, what is intended is one having less than 0.5 g.
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` ~78249 .
phytate per 100 g. of solids, and preferably less than 0.3 ~. phytate per 100 g. of solids. As the pll is increased, the tendency to hydrolyze the protein and effect condensation through the sulfur contai~ing amino acids increases. While phytate removal takes place at all pH values in excess of pH 10.1, it is more efficient at pH values in excess of p~ 11Ø It is preferred to operate ln the range of about pl~ 12, and more preferably at p~l 11.4-11.8 to avoid as much as possible a loss in protein quality due to hydrolysis or condensation of sulfur-contalning amino acids, and still effect efficient removal of phytate. O
! The temperature during phytate separation following alkaline treatment should preferably be at lea~t 10C., for instance 10C. to 50C. or 15C. to 30C. It has been found that removal of phytate is incomplete but, nevertheless, significant at 10C. or lo~er following alkaline treatment at pH 11-12. At 10C. approximately one-half of the phytate is removed, while at 20C. 90% of the phytate is removed, and at 30C. more than 99% removal is effected. The foregoing temperature ranges are the optimum values for dissociation of the soluble soy protein phytic acid complex and for rendering of the phytates and phytic acid derivatives insoluble. Under some manu-facturing conditions, however, other temperature ranges may prove to be more suitable since the temperature at which the phytate precipitate is formed has an effect on the physical nature thereof which affects its filtration and centrifugation characteristics.
Empirical selection of the optimum phytate insolubilization tempera-ture for any given manufacturing arrangement is desirable. Optimum values usually fall within the range of 15C. to 30C. At tempera-tures in excess of 50C. the tendency for hydrolysis of the pFotein, :' ' -1~78Z49 and for the formatlon of undesirable proteln rcaction products increa~ses, the higher tcmperatures are thus to be avoided.
The time of exposure of the soy protein containing extract to aqueous base ~n the range of p~l 10.6-14 durlng phytate precipitation S should be limited according to the temperature employed so that substantial loss in protein quality does not occur. A convenient way to ascertain this is to determine the cysteine content of the protein since cyqteine is the most sensitive of the amino acids to loss from the soy protein under the alkaline conditions employed.
It has been found that at pU 11 and at temperatures in the range of 20-30C. eæsentially no loss of cysteine occurs during periods of up to 6-3/4 hours. However, at pH 12, significant loss of cysteine i occurs within 2-3/4 hours at 40C. At 20C. and pH 12 the loss of cysteine is not believed ~o be significant during 2-3/4 hours, but after 6-3/4 hours, approximately 15% of the cysteine is lost.
Accordingly, a period of up to about 1/2 hour for phytate precipi-tstion is recommended, but longer periods are satisfactory when operating at the lower end of the pH range of about pH 11. At pH values of 12 and higher careful limitation of the time of exposure to the alkaline medium should be exercised by moni~oring the content of the amino acid cysteine.
In summary, the duration of exposure of the alkaline aqueous ex~ract of soybean material in the range of pH 10.6-14 for the purpose of phytate precipitation should be chosen so that under the conditions of pH and temperature employed the duration of exposure is such that not more than about 10% of the cysteine of the 50y protein containing extract is destroyed. Treatment conditions resulting in substantially .~ .
`` 249 more cystelne destructlon than 10% are regarded as inapproprlate since one of the ob~ects of the present invention i9 to provide a soy protein of lmproved nutritional quality whlch purpose ls defeated by degradation of the soy proteln and loss of certain amino acid values, particularly cysteine.
Step (b) SeParatiOn of Particulate Material.- Step (b) involves separation of the spent fla~es and of the insolubili~ed `phytate when the process i9 operated in such a manner as to insolu-bilize phytate from the extract. There is obtained an aqueous emulslon of susper,ded lipid materlal whlch may contain suspen~e~
protein, as well as dissolved protein, and dissolved carbohydrate.
Conventional solld separation unit processes may be employed such as centrifugation. The same constraints on time, temperature and pH which are applicsble durlng formation of the extract in step (a) are applicable during separation of the particulate material in step (b).
The aqueous emulsion of soybean lipld from which partlculate material has been removed is most convenient for further processing if it contains from 1-12% by weight of protein, 1-10% by weight of carbohydrate and associated mineral constituents which are dlssolved during the extraction process. If extracts are prepared containing more than 12% by weight of protein, they are ~enerally viscous and both inconvenient to handle and inefficiently procèssed in the centrifugation or filtration and washing steps.
In one preferred mode of operation, the emulsion produced in step (b) is sub~ected to high-temperature short-time heat treatment at a pH of less than pH 10 but greater than the isoelectrlc value of , . .
~C~78249 .. .
the soy proteln, for ins~ance pll 6-10, and preferably pH 7Ø A
tempera~u~'e in thc range of from 60C. to 150C. for a period of from 1 sec. to 30 mln. is employed. The selection of the proper combination of time ~nd temperat:ure is discussed in more detall ~ 5 below. Ileat treatmen~ at this Rtage has the bencfit ol lncreasing ; the ultrafiltration ~lux rate ln step (c) an-l o reducing the mlcrobial population sufficiently ~o eliminate spoilage durlng the ultrafiltration fitep.
SteP ~ _hydrate Separation.- Filtration in step (c) 10 ig prlferably carrie~ out usin~ a so-called ultrafiltration apparaLus containing a semi-permeable membr~ne which wlll retain protein con-; stituents, and allow dissolved lower molecular wcight materlals to pass.
Seml-permeable membranes having the capability of retaining protelns having a minimum molecular weight in the range of abou~ 10,000-; lS 50,000 daltons are useful. The apparatus is operated at a gauge press~re of about 25 psig but pressures in the range of about 15 to 100 psls and hlgher are useful. Ultraflltra~ion according to the pre--sent inventlon is to be distinguiYhed from o~her membrane filtration proccsses in respect o~ the porosity of the mar.~brane employet 20 ant the pressure m~intained on the retentate to force passage of exces~ water and low molecular weight ingredients. Reverse "' 08mo6is processes, for example, use membranes having much lower porosity and retain much lower molecular weight materials such ~' ' 88 the carbohydrate constltuen1-s of the soybean which it is ,, desired to eliminate by the present process. Reversc osmosis ; processes are also considerably more. expensive to operate in ~ that hi~her operatin~ pressures and generally lower flux rates 7 ~re involved.
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~078249 We have made the surprising dlscoveries that the prescnce of suspended or emulslficd fat in the extract from whlch the carbo-hydrates are to be removed by ultrafiltration does not interfere with the efficiency of the ultrafiltration and that the suspended or S emulsified fat remains in the retentate. Thus, it is possible to prepare a highly desirable nutritional product containing both fat and protein and little carbohydrate. The carbohydrates have long been known to be amonR the undesirable constituents of the soybean from the standpoint of human consumption.
Filtration employing a semi-permeable membrane is ~referably carried out at a pH in the range of pH 6.5 to pH 7.5 for the purpose of maintaining protein inte~rity but this is not essential. At pH values in excess of pH lO some filtration membranes may be subject to deterioration or damage and, furthermore, a loss in protein quality is more likely to occur. Therefore, it is preferred to conduct the membrane filtration step at a pH in the range of about pH 6-10, more preferred at pH 6.5 to pH 7.5, and, ln any event, at a pH in excess of the isoelectric range of the protein.
The suspension which is subjected to ultrafiltration and the retentate during the ultrafiltration process is preferably malntained a~ a temperature in the range of about 45C. to 75C.
to improve the flux rate and to minimize bacterial spoilage.
With respect to the latter point, a temperature of at least about 25 60-65C. is preferredO Temperatures in excess of 75C. are undesirable since chemical decomposltion and condensation reactions of the protein occur with the formation of undesirable byproducts - .
1(~78249 and loss in protein quallty. Below about 60C. pasteurization is less effective and spoilage may occur. Below about 45C. the benefit to flux rate lmprovement diminishes.
~ It is preferred to produce a final liquid soy lipid-protein comestible having a protein concentration of about 3% to 7% by weight, but for some purposes lower or higher concentrations may be desirable.
The proteln concentratlon of the soy protein can be readily ad~usted to any value in the range of 1% to 12% by weight by appropriate manlpulation of volumes of extraction water, permeate collected, or evaporative concentration or dilution may be employed as long9as the protein remains in solution. Protein solutions having concentrations of less than 1% by wei~ht are uneconomical and of little practical lnterest. For instance, when commencing with a particle-free emulsion having a protein concentration of 3.5~, removal of half of the volume as permeate results ln a retentate having a protein ; concentratlon of 7%. ~ substantial reduction in carbohydrate and mineral content occurs through elimination of these ingredients wlth the permeate water. Since the soybean carbohydrate substituents are generally undesirable nutritional ingredients due to their dlfficulty of digestion by man, lt ls desirable to eliminate a ma~or proportion thereoi.
We have expressed the carbohydrate content of the soybean lip$d-protein comestibles prepared ln our present studies as protein coefficient which is the ratio of the protein content thereof to the total of the protein and carbohydrate content. For infant formula use we prefer a protein coefficient of about 0.90 or more since the soyb=an carbohydrates ~ause flatulents and undes1rab1e stoo1s ~078Z49 ln infants subsisting on the soy proteln based formula. ~queous llpld-protein comestibles havin~ proteln coefflcients of about 0.8 are suitable for the fortification of conventional foods 8uch as meat and bread and for the preparation of liquld dietary products for more mature sub~ects.
It has been found tlat by concentration of a 3.5~ by weight protein containing extract by ultrafiltration to one-half of its original volume that the retentate still contains an undesirably high proportion of carbohydrate for infant formula use. Such product is suitable for certain other food uses, however. I~e O
have found that diafiltration (a form of ultrafiltration in which the retentate i6 continuously diluted with water or a wash solution) is an appropriate way of eliminating additlonal undesired carbo-hydrate and mineral constituents. This amounts simply to continuously adding a diafiltration solution, preferably water, to the retentate as it is circulated through the filtration apparatus and permeate is removed. Diafiltration thus constitutes a washing operation in whlch the undeslred low molecular weight constituents are washed from the retentate.
Referring to the original volume of particulate-free emulslon as one ln a preferred form of the process, ~ volume of permeate is removed by ultrafiltration and then from ~ to 2'~
volumes of water are used for dilution of the retentate during diafiltration until the total permeate collected i9 Up to 3 volumes.
Dilafiltration to provide a larger permeate volume affords little additional purification. Diafiltration may be commenced at a gradual rate near the beginning of the ultrafiltration, and the .' ~ ' . ' ' rate increased as the desired protein concentration is approached, or alternatively, concentratlon to the desired protein content may precede diafiltration.
Instead o water, diafiltration solutions containing desired ingredients for the final product, or which improve protein retention or flux rate may be employed. In the case of lnfant formula products, additional ingredients of the flnal formulated product which contain ~he present soy protein solution as a principle protein ingredient which may be combined therewith ~ 10 during the diafiltration stage include carbohydrate, fat, ando ; mineral constituents. While this may offer an advantage in some instances, it is generally not a preferred mode of operation since at least a portion of these additives will be lost to the permeate by passage through the membrane. These losses can in part be offset by recovery of the desired ingredients from the permeate or by recycling the permeate to the diafiltration water.
A desirable ad~unct to the process constituting an additional novel feature of the invention involves high-temperature short-time (HTST) heat treatment of the extract, and/or retentate, and/or of a liquid dietary product formed from the latter. This - modification, constituting a preferred version of the present invention, has several purposes. When conducted prior to ultra-filtration, heat treatment has the benefit of reducing the bacterial ^ count and minimizing the risk of spoilage of the clarified extract during further processing including ultrafiltration. It has the further benefit of facilitating the ultrafiltration step since it has been found that the flux rate at which permeate is formed during ,~
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1~78Z4g ultrafiltration is increased when the partlculate-free emulsion ls beated prior to ultrafiltration. High-temperaturc short-time heat treatment whcn used in conJunction with ultrafiltration to produce a lipid-protein comestible is considered part of the S present invention as are the protein isolates produced thereby.
The latter may be formulated as is with the protein in the dissolved state, or they may be dried.
From the standpoint of the utility of the aqueous lipid-protein comestib~e of the present invention in forming liquid : 10 dietary products such as infant formulas, milk substitutes, an,dmeal replacements or supplements, heat treatment has the benefit of improving the nutritional quality of the protein, and of improving the functlonality of the protein including a reduction of the viscosity of solutions thereof, and improvement in solubility 15 and fat emulsification properties. These benefits are derived ' whether heat treatment takes place before or after ultrafiltration.
The time and temperature conditions which are operable for the foregoing purposes do not lend themselves to precise definition, but those skilled in the milk treatment and soy protein g 20 extraction arts will have no difficulty in selecting optimum conditions for the particular manufacturing facilities which are ; availsble. Broadly speaking, the higher the temperature employed, the shorter tbe time of treatment with the maximum temperature presently considered applicable being about 150C. for a period 25 of 1 sec. ~h`en lower temperatures are employed, longer time periods of treatment are necessary, for instance 60C. for about 30 min.
has substantially equivalent effect to 150C. for 1 sec. Other : ~:
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, 1~78249 suitable times and temperatures including 130C. for 45-60 secs.
and 100C. for 10 min.
In one preferred mode of the short-term high-temperature ; heat treatment modificatlon of the process, the heat treatment step S is divided so that a relatively mild heat treatment is employed prior to ultrafiltration for the purpose of reducing spoilage and improving flux rate, and then a more severe heat treatment i9 employed on the finlshed soy protein retentate after removal of the carbohydrate constituents. This has the advantage of minimiYing the brownlng reaction which results from an interaetion of the soybean carbohydrate with the soy protein which has a tendency to occur when carbohydrate containing soy protein extracts ; are heated. For example, the clarified extract Just prior to ultra-filtration may be given a mild heat treatment of from about 60C. for 15 30 min. to 130C. for l min., cooled to a temperature of about 45-75C.
and then purified by ultrafiltration as is described above. The ~, resulting aqueous purified soy protein solution retentate may be then given a further more severe heat treatment for the purpose of improving the functionality of the protein and destroying anti-nutritional factors. For this second heat treatment, a temperature in the range of about 110C. for 1 min. up to about 150C. for 1 sec.
may be employed. The second heat treatment may be incorporated with subsequent process steps whereby a liquid dietary product is produced i from the aqueous purified soy protein by combining other ingredients:' therewith.
The preferred heat treatment conditions for a given appli-cation of the process are determined empirically and adapted to the :~
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--^-~078249 avallable equlpment by evaluatlng ~he performance of the heated extract when heatlng is carried out for dif~erent time periods and at different temperatures. For some purposes, one set of heat treatment conditions may be preferred while another set may be 5 preferable when the resulting aqueous purified soy protein ~ ;
solution is to be used for a different purpose. In any event, the conditions are selected to achieve one or more of the following results:
(i) improving the protein efficiency ratio of said lipid-protein comestible produced in step ~c), or of a liquid dietary product prepared therefrom;
(ii) improving the functionality of said lipid-protein comestible produced in step (c) or of a liquid dietary product prepared therefrom as measured by sedimentation :~.
lndex, ni~rogen solubility index, or emulsion stability index, (iii) increasing the ultrafiltration flux rate in step (c), or (iv) reducing the microbial population of said particulate free emulsion and said retentate sufficiently to substantially eliminate spoilage thereof during ultrafiltration in step (c).
For food applications, the liquid lipid-protein comestible produced as retentate according to the process described above may be dried by conventional methods including freeze-drying and spray-drying, and the dry powder used as a food ingredient. For the preparation of beverages such as soy milks, the retentate without .,:
,,i :
~78Z49 drying is preferably comblned with other desired ingredients such as carbohydrates, fats, vitamins, minerals, etc. and the coml)osition homo~en~zed and, if desired, canned and sterilized. The food products and bevcrages have improved nutritional value, stabllity, and functional qualities.
Description of Specific Embodiments ExamPle 1.- Seed grade soybeans were ground twice in a hammermill employing a very slow feed rate to prevent the development of excessive heat to provide a coarse flour. The tempreature of the flour at the end of each grinding period was 44C. A suspension of 250 g. of the ground beans in 4 1. of deionized water at room temperature was prepared in a vessel equipped for mechanical agitation and the pH of the suspension was adjusted to pH 9.0 by addition of 10% aqueous sodium hydroxide. The suspension was thoroughly mixed at this pH and at room temperature for 30 min. and the insoluble material was then separated by centrifugation at 4022 x G. The supe matant liquid was again transferred to the vessel equipped with the agitator and adjusted to pH 11.6 wlth 10% aqueous sodium hydroxide and mixing at room temperature was continued for another 30 min. period. ~ -20 The suspension was then centrifuged at 13,218 x G and the supernatant liquid comprising an emulsion of the soybean lipid-protein in a solution of soy protein and soy carbohydrate was subjected to ultrafiltration at 46C. and 40 psi. employing a semi-permeable membrane capable of retaining proteins having molecular weights ; 25 in excess of 30,000 daltons. The emulsion was concentrated by ultra-; filtration to one-half of its original volume~ and then further .
,.
`\
purified by diafiltration involving dilution of the concentrated retentate wlth deioni~ed wa~er at the same raee that permeate was being collected so as to maintain the volume of the retentate constant.
A volume of diafiltration water equal to the orlginal volume of the emulsion charged to the ultrafiltration apparatus was employed. The retentate was then freeze dricd and analyzed. The results obtained are given in the following table along with the results of four other examples conducted in similar fashion but employing either different pH values and times for extraction or employing commercial full 1~ fat soy flour as raw material rather than ground whole soybean.
., .
~o7~3z49 C~ .
~ o . ~ o o~
~o ~ o U~
.: o o C:> _ .~ o , ~.
.
p~ ;~ u~ CO
~ ~ O ~ ~
~ ~ . .
~1 ~1 , ,, ~o ~ ~, o o o o o l l .
,.,,, I
I
;. .
., ~ P~ P~ a~
a o "~ ~ R
vl o ~o g o , ~ r ... .
E3 ol ~
x ~1 o ':
1078;~49 The protein coefflcient is a measurc of the rclatlve removal of carbohydrate and retention of protein by the membrane filtratlon step. The protcln cocfficlent ls the ratlo of the proteln content on a welght basis of the product to the sum of the protein content and carbohydrate content on a welght basis.
Protein was determined by the method of Lowry, et al., Journal of Biological Chemistry, 193:265-275 (1951) and carbohydrate was determ~ned by the method of Dubols, et al., Analytlcal Chemlstry 28:350-356 (1956). Phytic acid was determlned by the method of 10 Wheeler, et al., Cereal Chemistry 48:312-320 (1971).
It is evident by comparison of the phytic acid composltion of the products of Examples 1 and 2 wlth that of Example 3 that extraction at pH 11.6 results in substantlal reductlon or virtual ellmination of phytic acid from the product. Phytlc acld removal was unsuccessful in Example #5 and the protein yields in Examples 4 and 5 were both substantially lower than in Examples 1-3. Carbo-hydrate removal was good ln all instances, however. Examples 4 and 5 employed commercial full fat soy flour as raw materlal whlch had been toasted by the manufacturer at about 65C. for 20-30 min.
2~ Since the freshly ground whole bean raw materlal employed in Examples 1-3 was not toasted in this fashion, it is believed that heat treatmen~ of the ground oilseed raw materlal prlor to extractlon ls undeslrable.
Example 6. Lipid-Protein Comestible From Wet-Ground l~ole 25 Sovbeans.- Soybeans, 625 g., were soaked in 10 1. of distilled water at 50C. for l hr. They were then transferred to a blender of the type having rotating knives borne on an axial shaft at the bottom _ 23 -~C~78;~49 of the c~ntalncr. The blender eol1~ainer had a capacity of 1 Kal.
and the grlnding wa~ carrled out at 50C. for 5 mln. The warm solution was then cooled to room te~lperature, 20-25C. and adJustcd to pH ll. 7 witll dilute aqueous sodium hydroxide. It w~s held at thi~ value for 15 mln. Ihe pH of the freshly ground beans was pH 6.4 prior to pH adJustment. Insoluble material was then removed by centrl~ugatiotl at 4000 x G. ln a desludging centrifnge 20 min. The light liquid stream from which most of the particulate materlal had been removed was again centrifuged in a Sorvall SZ-14GK
10 continuous f]ow through centrifuge head at 10,000 x G to remove further parti1ulate Qa~erial. The resulting emulsion of liquid material containing dissolved protein and dissolved carbohydrate at pH 11.3 wae adJusted to pH 7.0 as it was collected. It wa~s kept at 4C. overnight and then purified by ultrafiltration. The par';iculate 15 free emulsion had a volume of 7.9 l. and contained 4.45% by weight of solids. Ultrafiltration was carried out with the same type of apparatus as is described in EY~ample 1 until 3.95 l. of permeate had been collected. Distilled water for diafiltration was then added to the retentate at the same rate as permeate was collected with diafil-tration in thls fashion being continued until a total of 11.97 kg.
of permealte had been collected. The retentate weighed 4.59 kg. and .~ ~
contained 5.42% by weight of collds. On a dry basis, the following analytical results were obtained. The values given are the average of three samples ~ith standard deviations repor~ed.
25 Protein (g./100 g. of sollds) 62.6 _ 0.379 Fat (g./100 g. of protein) 49.8 + 12.4 Ash (g./100 g. of protein) 3.32 1 0.153 Phytic Acld (g./100 g. of proteln) 0.082 -' ~A 24 -..
' . . . :
1~78249 . . .
Exam~le 7. Sov Mllk From ~ole Bean Lipid-Proteln.-A batch of the lipld-protein comestlble retentate prepared according to the method described ln Example 6 welghing 2.08 kg. and having the analysis shown was combined in the liquid state wlth the followlng ingredients to yield a soy milk containlng 3.30% by welght of protein,
Example 6. Lipid-Protein Comestible From Wet-Ground l~ole 25 Sovbeans.- Soybeans, 625 g., were soaked in 10 1. of distilled water at 50C. for l hr. They were then transferred to a blender of the type having rotating knives borne on an axial shaft at the bottom _ 23 -~C~78;~49 of the c~ntalncr. The blender eol1~ainer had a capacity of 1 Kal.
and the grlnding wa~ carrled out at 50C. for 5 mln. The warm solution was then cooled to room te~lperature, 20-25C. and adJustcd to pH ll. 7 witll dilute aqueous sodium hydroxide. It w~s held at thi~ value for 15 mln. Ihe pH of the freshly ground beans was pH 6.4 prior to pH adJustment. Insoluble material was then removed by centrl~ugatiotl at 4000 x G. ln a desludging centrifnge 20 min. The light liquid stream from which most of the particulate materlal had been removed was again centrifuged in a Sorvall SZ-14GK
10 continuous f]ow through centrifuge head at 10,000 x G to remove further parti1ulate Qa~erial. The resulting emulsion of liquid material containing dissolved protein and dissolved carbohydrate at pH 11.3 wae adJusted to pH 7.0 as it was collected. It wa~s kept at 4C. overnight and then purified by ultrafiltration. The par';iculate 15 free emulsion had a volume of 7.9 l. and contained 4.45% by weight of solids. Ultrafiltration was carried out with the same type of apparatus as is described in EY~ample 1 until 3.95 l. of permeate had been collected. Distilled water for diafiltration was then added to the retentate at the same rate as permeate was collected with diafil-tration in thls fashion being continued until a total of 11.97 kg.
of permealte had been collected. The retentate weighed 4.59 kg. and .~ ~
contained 5.42% by weight of collds. On a dry basis, the following analytical results were obtained. The values given are the average of three samples ~ith standard deviations repor~ed.
25 Protein (g./100 g. of sollds) 62.6 _ 0.379 Fat (g./100 g. of protein) 49.8 + 12.4 Ash (g./100 g. of protein) 3.32 1 0.153 Phytic Acld (g./100 g. of proteln) 0.082 -' ~A 24 -..
' . . . :
1~78249 . . .
Exam~le 7. Sov Mllk From ~ole Bean Lipid-Proteln.-A batch of the lipld-protein comestlble retentate prepared according to the method described ln Example 6 welghing 2.08 kg. and having the analysis shown was combined in the liquid state wlth the followlng ingredients to yield a soy milk containlng 3.30% by welght of protein,
3.50% by welght of fat, and 5.00% by weight of carbohydrate.
In~redient Amount Whole bean protein material, liquid (total solids, 6.76%; protein, 4.26~; fat, 2.10%;
all by weight 1080.00 g.
Soy oil 47.04 g Corn syrup solids 23.96 g.
Sucrose 92.03 g.
Milk salts 21.90 g.
Magnesium chloride hexahydrate 2.11 g.
Carragèenan 1.26 g.
Lecithin 10.04 g.
Water, q.s. 2511.20 g.
All of the ingredients were comblned except the leclthin ~ 20 and the soy oll. The mixture was then heated to 66C. and the soy ; oil and lecithin mixture also heated to this temperature were added thereto and the mixture homogenized twice in a mechanical homogenizer st 3,000 psi. The homogeneous milk-like product was then bottled in 4 oz. nursing bottles and sterilized at 127~C. for 6 min. Samples were stored at room temperature. No difficulty in processing the formulstion was encountered.
.
In~redient Amount Whole bean protein material, liquid (total solids, 6.76%; protein, 4.26~; fat, 2.10%;
all by weight 1080.00 g.
Soy oil 47.04 g Corn syrup solids 23.96 g.
Sucrose 92.03 g.
Milk salts 21.90 g.
Magnesium chloride hexahydrate 2.11 g.
Carragèenan 1.26 g.
Lecithin 10.04 g.
Water, q.s. 2511.20 g.
All of the ingredients were comblned except the leclthin ~ 20 and the soy oll. The mixture was then heated to 66C. and the soy ; oil and lecithin mixture also heated to this temperature were added thereto and the mixture homogenized twice in a mechanical homogenizer st 3,000 psi. The homogeneous milk-like product was then bottled in 4 oz. nursing bottles and sterilized at 127~C. for 6 min. Samples were stored at room temperature. No difficulty in processing the formulstion was encountered.
.
Claims (33)
1. The process for preparing an oilseed lipid-protein comestible which comprises:
(a) forming an aqueous suspension of edible oilseed containing suspended oilseed lipid, dissolved oilseed protein, and dissolved oilseed carbohydrate at a pH in excess of the isoelectric range of said protein, said suspension being obtained by aqueous extraction of particulate oilseed material containing lipid, protein, and carbohydrate at a pH in excess of the isoelectric range of said protein;
(b) separating particulate material from said suspension to yield an emulsion containing suspended lipid, dissolved protein, and dissolved carbohydrate; and (c) separating carbohydrate from said emulsion by filtration employing a semi-permeable membrane which has the capability to retain suspended lipid and dissolved protein as retentate, and to pass dissolved carbohydrate as permeate.
(a) forming an aqueous suspension of edible oilseed containing suspended oilseed lipid, dissolved oilseed protein, and dissolved oilseed carbohydrate at a pH in excess of the isoelectric range of said protein, said suspension being obtained by aqueous extraction of particulate oilseed material containing lipid, protein, and carbohydrate at a pH in excess of the isoelectric range of said protein;
(b) separating particulate material from said suspension to yield an emulsion containing suspended lipid, dissolved protein, and dissolved carbohydrate; and (c) separating carbohydrate from said emulsion by filtration employing a semi-permeable membrane which has the capability to retain suspended lipid and dissolved protein as retentate, and to pass dissolved carbohydrate as permeate.
2. The process of Claim 1 wherein said oilseed is selected from the group consisting of chickpea, rapeseed, coconut, cottonseed, peanut, safflower seed. sesame seed, soybean, and sunflower seed.
3. The process of Claim 1 wherein said oilseed is soybean.
4. The process of Claim 3 wherein said particulate oilseed material in step (a) comprises ground soybean.
5. The process of Claim 3 wherein said particulate oilseed material in step (a) comprises fat-containing soybean flour.
6. The process of Claim 1 wherein said filtration employing a semi-permeable membrane in step (c) includes diafiltration.
7. The process of Claim 6 wherein diafiltration is continued until said retentate has a protein coefficient of at least about 0.8.
8. The process of Claim 6 wherein said diafiltration is continued until said retentate has a protein coefficient of at least about 0.9.
9. The process of Claim 1 wherein said emulsion and said retentate in step (c) are maintained at a temperature within the range of about 45°C. to 75°C. during membrane filtration.
10. The process of Claim 3 wherein said forming an aqueous suspension in step (a) and said separating particulate material in step (b) are conducted at a pH in excess of pH 10.1.
11. The process of Claim 10 wherein steps (a) and (b) are carried out at a temperature in excess of about 10°C.
12. The process of Claim 10 wherein steps (a) and (b) are carried out at a temperature in the range of about 15°C. to about 30°C.
13. The process of Claim 10 wherein said pH is within the range of pH 11 to pH 12.
14. The process of Claim 3 wherein said forming an aqueous suspension in step (a) and said separating particulate material in step (b) is conducted at pH 10 or less.
15. The process of Claim 14 wherein said pH is within the range of pH 7-9.
16. The process of Claim 3 wherein said filtration employing a semi-permeable membrane in step (c) is conducted within the range of pH 6.5 to pH 7.5.
17. The process of Claim 3 wherein step (b) includes heating said emulsion at a temperature of from 60°C. to 150°C. for a period sufficient to:
(i) improve the protein efficiency ratio of said lipid-protein comestible, (ii) improve the functionality of said lipid-protein comestible as measured by sedimentation index, nitrogen solubility index, or emulsion stability index, (iii) increase the ultrafiltration flux rate in step (c), or (iv) reduce the microbial population of said emulsion produced in step (b) sufficiently to substantially eliminate spoilage thereof during filtration employing a semi-permeable membrane in step (c) said emulsion having a pH in excess of the isoelectric value of said protein but less than pH 10 during said heating.
(i) improve the protein efficiency ratio of said lipid-protein comestible, (ii) improve the functionality of said lipid-protein comestible as measured by sedimentation index, nitrogen solubility index, or emulsion stability index, (iii) increase the ultrafiltration flux rate in step (c), or (iv) reduce the microbial population of said emulsion produced in step (b) sufficiently to substantially eliminate spoilage thereof during filtration employing a semi-permeable membrane in step (c) said emulsion having a pH in excess of the isoelectric value of said protein but less than pH 10 during said heating.
18. The process of Claim 17 wherein said period is from 1 sec.
to 30 min.
to 30 min.
19. The process of Claim 17 wherein said heating is at a temperature in the range of from 60 C. to 130°C. for a period of from 45 sec. to 30 min.
20. The process of Claim 3 wherein said retentate produced in step (c) 18 heated at a temperature in the range of from 60°C. to 150°C. for a period sufficient to (i) improve the protein efficiency ratio of said retentate, or (ii) improve the functionality of said retentate as measured by sedimentation index, nitrogen solubility index, or emulsion stability index.
21. The process of Claim 20 wherein said retentate is combined with additional nutritional ingredients before heating.
22. The process of Claim 20 wherein said period is from 1 sec. to 30 min.
23. The process of Claim 20 wherein said temperature is in the range of from 60°C. to 130°C. and said period is from 45 sec.
to 30 min.
to 30 min.
24. The process for preparing a liquid food product containing oilseed protein and oilseed fat wherein said oilseed protein constitutes the principle protein ingredient of said product which comprises combining said retentate produced by the process of Claim 1 with other nutritional ingredients.
25. The process of Claim 1 wherein said retentate produced in step (c) is dried.
26. The product produced by the process of Claim 1.
27. The product produced by the process of Claim 3.
28. The product produced by the process of Claim 10.
29. The product produced by the process of Claim 14.
30. The product produced by the process of Claim 17.
31. The product produced by the process of Claim 20.
32. The product produced by the process of Claim 24.
33. The product produced by the process of Claim 25.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/743,246 US4088795A (en) | 1976-11-19 | 1976-11-19 | Low carbohydrate oilseed lipid-protein comestible |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078249A true CA1078249A (en) | 1980-05-27 |
Family
ID=24988062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA288,944A Expired CA1078249A (en) | 1976-11-19 | 1977-10-18 | Low carbohydrate oilseed lipid-protein comestible |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4088795A (en) |
| JP (1) | JPS5366455A (en) |
| AU (1) | AU512281B2 (en) |
| BE (1) | BE860873A (en) |
| CA (1) | CA1078249A (en) |
| CH (1) | CH634468A5 (en) |
| CY (1) | CY1214A (en) |
| DE (1) | DE2751572A1 (en) |
| FR (1) | FR2371151A1 (en) |
| GB (1) | GB1575336A (en) |
| HK (1) | HK26084A (en) |
| KE (1) | KE3348A (en) |
| MY (1) | MY8500143A (en) |
| NL (1) | NL7712677A (en) |
| NZ (1) | NZ185306A (en) |
| PH (1) | PH13373A (en) |
| SE (1) | SE435232B (en) |
| SG (1) | SG69283G (en) |
| ZA (1) | ZA776847B (en) |
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| US10645950B2 (en) | 2017-05-01 | 2020-05-12 | Usarium Inc. | Methods of manufacturing products from material comprising oilcake, compositions produced from materials comprising processed oilcake, and systems for processing oilcake |
| US20190183155A1 (en) * | 2017-05-01 | 2019-06-20 | Usarium Inc. | Upcycling solid food wastes and by-products into human consumption products |
| EP3941212A1 (en) | 2019-03-19 | 2022-01-26 | Unilever IP Holdings B.V. | Frozen confection |
| US11839225B2 (en) | 2021-07-14 | 2023-12-12 | Usarium Inc. | Method for manufacturing alternative meat from liquid spent brewers' yeast |
| CN115286725B (en) * | 2022-08-31 | 2023-06-02 | 山东万邦赛诺康生化制药股份有限公司 | Preparation method of high-purity low-molecular-weight heparin |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288614A (en) * | 1964-11-02 | 1966-11-29 | Pacific Union Ass Of Seventh D | Process of producing milk from soy beans |
| US3632346A (en) * | 1968-04-30 | 1972-01-04 | Rohm & Haas | Process for rendering innocuous flatulence-producing saccharides |
| US3622556A (en) * | 1969-09-08 | 1971-11-23 | Procter & Gamble | Preparing light-colored protein isolate from sunflower meal by alkali extraction under an inert gas blanket followed by membrane ultrafiltration |
| US3653912A (en) * | 1969-12-22 | 1972-04-04 | Gen Mills Inc | Preparation and use of a bland dispersible food protein |
| GB1318596A (en) * | 1970-10-09 | 1973-05-31 | Unilever Ltd | Extraction of protein from seed |
| US3736147A (en) * | 1971-04-05 | 1973-05-29 | Coca Cola Co | Process for preparing protein products |
| US3732395A (en) * | 1971-06-22 | 1973-05-08 | Du Pont | Yarn heater |
| US3728327A (en) * | 1972-04-10 | 1973-04-17 | Grain Processing Corp | Protein and method of extracting same from soybeans employing reverse osmosis |
| US3809771A (en) * | 1972-08-08 | 1974-05-07 | Agriculture | Process for obtaining full-fat oilseed-protein beverages |
| US3901978A (en) * | 1972-08-21 | 1975-08-26 | Univ Illinois | Soybean beverage and process |
| FR2215174A1 (en) * | 1973-01-26 | 1974-08-23 | Grain Processing Corp | Soya proteins - of good quality extracted in high yields using reverse osmosis |
| FR2257230B1 (en) * | 1973-09-14 | 1976-11-19 | Agronomique Inst Nat Rech | |
| US3995071A (en) * | 1975-06-23 | 1976-11-30 | Mead Johnson & Company | Aqueous purified soy protein and beverage |
-
1976
- 1976-11-19 US US05/743,246 patent/US4088795A/en not_active Expired - Lifetime
-
1977
- 1977-09-29 AU AU29210/77A patent/AU512281B2/en not_active Expired
- 1977-09-30 NZ NZ185306A patent/NZ185306A/en unknown
- 1977-10-18 CA CA288,944A patent/CA1078249A/en not_active Expired
- 1977-11-08 JP JP13403277A patent/JPS5366455A/en active Granted
- 1977-11-14 SE SE7712847A patent/SE435232B/en not_active IP Right Cessation
- 1977-11-16 FR FR7734440A patent/FR2371151A1/en active Granted
- 1977-11-16 ZA ZA00776847A patent/ZA776847B/en unknown
- 1977-11-16 BE BE182657A patent/BE860873A/en not_active IP Right Cessation
- 1977-11-16 PH PH20439A patent/PH13373A/en unknown
- 1977-11-17 NL NL7712677A patent/NL7712677A/en not_active Application Discontinuation
- 1977-11-18 DE DE19772751572 patent/DE2751572A1/en active Granted
- 1977-11-18 CY CY1214A patent/CY1214A/en unknown
- 1977-11-18 GB GB48111/77A patent/GB1575336A/en not_active Expired
- 1977-11-21 CH CH1418877A patent/CH634468A5/en not_active IP Right Cessation
-
1983
- 1983-11-11 SG SG692/83A patent/SG69283G/en unknown
- 1983-11-16 KE KE3348A patent/KE3348A/en unknown
-
1984
- 1984-03-22 HK HK260/84A patent/HK26084A/en unknown
-
1985
- 1985-12-30 MY MY143/85A patent/MY8500143A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU512281B2 (en) | 1980-10-02 |
| KE3348A (en) | 1983-12-16 |
| CY1214A (en) | 1984-04-06 |
| CH634468A5 (en) | 1983-02-15 |
| NL7712677A (en) | 1978-05-23 |
| HK26084A (en) | 1984-03-30 |
| MY8500143A (en) | 1985-12-31 |
| DE2751572A1 (en) | 1978-05-24 |
| JPS5366455A (en) | 1978-06-13 |
| FR2371151B1 (en) | 1984-08-10 |
| GB1575336A (en) | 1980-09-17 |
| JPS6133544B2 (en) | 1986-08-02 |
| SG69283G (en) | 1984-08-03 |
| DE2751572C2 (en) | 1989-08-03 |
| BE860873A (en) | 1978-05-16 |
| ZA776847B (en) | 1978-09-27 |
| PH13373A (en) | 1980-03-20 |
| AU2921077A (en) | 1979-04-05 |
| NZ185306A (en) | 1981-03-16 |
| SE435232B (en) | 1984-09-17 |
| SE7712847L (en) | 1978-05-20 |
| FR2371151A1 (en) | 1978-06-16 |
| US4088795A (en) | 1978-05-09 |
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