CA1055931A - Process for the recovery of protein having improved solution clarity - Google Patents
Process for the recovery of protein having improved solution clarityInfo
- Publication number
- CA1055931A CA1055931A CA220,257A CA220257A CA1055931A CA 1055931 A CA1055931 A CA 1055931A CA 220257 A CA220257 A CA 220257A CA 1055931 A CA1055931 A CA 1055931A
- Authority
- CA
- Canada
- Prior art keywords
- protein
- phosphate
- solution
- aqueous solution
- proteinaceous
- 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
Links
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 72
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011084 recovery Methods 0.000 title claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 147
- 239000010452 phosphate Substances 0.000 claims abstract description 146
- 239000000243 solution Substances 0.000 claims abstract description 127
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 74
- 239000002244 precipitate Substances 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000001205 polyphosphate Substances 0.000 claims abstract description 22
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 22
- 125000000129 anionic group Chemical group 0.000 claims abstract description 17
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 17
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 17
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000007935 neutral effect Effects 0.000 claims abstract 2
- 108010046377 Whey Proteins Proteins 0.000 claims description 104
- 102000007544 Whey Proteins Human genes 0.000 claims description 102
- 235000018102 proteins Nutrition 0.000 claims description 66
- 235000013351 cheese Nutrition 0.000 claims description 61
- 239000005862 Whey Substances 0.000 claims description 59
- 235000021119 whey protein Nutrition 0.000 claims description 45
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 9
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052783 alkali metal Chemical group 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 3
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 3
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 claims description 3
- CQAIPTBBCVQRMD-UHFFFAOYSA-L dipotassium;phosphono phosphate Chemical compound [K+].[K+].OP(O)(=O)OP([O-])([O-])=O CQAIPTBBCVQRMD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000002378 acidificating effect Effects 0.000 abstract description 17
- 235000013361 beverage Nutrition 0.000 abstract description 17
- 239000010414 supernatant solution Substances 0.000 abstract description 12
- 238000012423 maintenance Methods 0.000 abstract description 2
- QURLONWWPWCPIC-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol;3,6-dichloro-2-methoxybenzoic acid Chemical compound NCCOCCO.COC1=C(Cl)C=CC(Cl)=C1C(O)=O QURLONWWPWCPIC-UHFFFAOYSA-N 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000012460 protein solution Substances 0.000 description 23
- 238000002834 transmittance Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 239000011550 stock solution Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 125000005341 metaphosphate group Chemical group 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 235000019830 sodium polyphosphate Nutrition 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- -1 for example Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960004838 phosphoric acid Drugs 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000006920 protein precipitation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 101800000263 Acidic protein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- 240000007930 Oxalis acetosella Species 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012888 bovine serum Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 235000013861 fat-free Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000021239 milk protein Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
- A23L2/66—Proteins
-
- 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
- A23J1/20—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from milk, e.g. casein; from whey
- A23J1/205—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from milk, e.g. casein; from whey from whey, e.g. lactalbumine
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2300/00—Processes
- A23V2300/30—Ion-exchange
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Biochemistry (AREA)
- Peptides Or Proteins (AREA)
- Dairy Products (AREA)
Abstract
PROCESS FOR THE RECOVERY OF PROTEIN
HAVING IMPROVED SOLUTION CLARITY
Abstract of the Disclosure A process for recovering protein having improved solution clarity at acid pH from proteinaceous aqueous solutions comprising admixing with a proteinaceous aqueous solution a phosphate to form a phosphate complexed solution, adjusting the pH of the phosphate complexed solution to a neutral range of from about 6.0 to about 8.0 by the addition of base to form a precipitate and a pretreated proteinaceous aqueous solution, separating the precipitate from the pretreated proteinaceous aqueous solution to provide a separated precipitate and a separated pretreated proteinaceous aqueous solution, admixing with the separated pretreated proteinaceous aqueous solution a medium chain length polyphosphate to form a protein-phosphate complexed solution, adjusting the pH of the protein-phosphate complexed solution to an acid range of from about 4.5 to about 2.0 by the addition of acid to form a protein-phosphate pre-cipitate and a supernatant solution, separating the protein-phosphate precipitate from the supernatant solution, dispersing the separated protein-phosphate precipitate in water having a final pH from about 5.0 to about 10.0 to form a protein-phosphate dispersion, contacting the protein-phosphate dispersion with an anionic ion exchange resin, and recovering the effluent containing protein. The effluent containing protein is useful for prepar-ing fortified acidic beverages, which require protein solubility and maintenance of clear solutions at acid pH.
HAVING IMPROVED SOLUTION CLARITY
Abstract of the Disclosure A process for recovering protein having improved solution clarity at acid pH from proteinaceous aqueous solutions comprising admixing with a proteinaceous aqueous solution a phosphate to form a phosphate complexed solution, adjusting the pH of the phosphate complexed solution to a neutral range of from about 6.0 to about 8.0 by the addition of base to form a precipitate and a pretreated proteinaceous aqueous solution, separating the precipitate from the pretreated proteinaceous aqueous solution to provide a separated precipitate and a separated pretreated proteinaceous aqueous solution, admixing with the separated pretreated proteinaceous aqueous solution a medium chain length polyphosphate to form a protein-phosphate complexed solution, adjusting the pH of the protein-phosphate complexed solution to an acid range of from about 4.5 to about 2.0 by the addition of acid to form a protein-phosphate pre-cipitate and a supernatant solution, separating the protein-phosphate precipitate from the supernatant solution, dispersing the separated protein-phosphate precipitate in water having a final pH from about 5.0 to about 10.0 to form a protein-phosphate dispersion, contacting the protein-phosphate dispersion with an anionic ion exchange resin, and recovering the effluent containing protein. The effluent containing protein is useful for prepar-ing fortified acidic beverages, which require protein solubility and maintenance of clear solutions at acid pH.
Description
Background of the Invention Generally, the invention relates to a new process for the recovery of protein having improved solution clarity at acid pH from proteinaceous aqueous solutions. More particularly, the invention relates to a new process for the recovery of protein having improved solvtion clarity at acid pH from cheese whey and the use thereof in the fortification of acidic beverages, which require protein solubility and solution clarity at acid pH.
It is known that most food products can be nutritionally improved by protein fortification. Proteins heretofore useful for protein fortification include for example, soy protein, casein, and cheese whey proteins. Recently, it has become desirable to nutritionally improve acidic beverages by protein fortification. However, protein fortification of acidic beverages has been especially difficult, since proteins exhibit decreased solubility and increased solution turbidity at acid pH.
Recently, there has been particular interest in the use of proteins recovered from cheese whey for protein fortifi-cation of acidic beverages. This interest relates to the acid solubility of undenatured cheese whey proteins, which remain in solution at acid pH during the cheese making process.
In addition to protein solubilitv at acid pH, protein fortification of acidic beverages requires the maintenance of solution clarity at acid pH. Therefore, even though a particular protein exhibits adequate acid-solubility, the use thereof in acidic beverages is prohibited if the solution clarity at acid pH is unsatisfactory under the conditions of use.
Generally, it is known that protein can be recovered from proteinaceous aqueous solutions by the phosphate precipi-tation of protein from the proteinaceous aqueous solution and the recovered protein can be made acid-soluble by the subsequent removal of phosphate ions by conventional methods, e.g., anionic ion exchange, electrodialysis, and the like. Specifically, it is known that precipitation of protein can be effected from pro-tenaceous aqueous solutions by metaphosphoric acid addition at acid pH. The precipitated protein can then be resolubilized by n the disassociation of the protein metaphosphate complex by the addition of an alkali, and the removal of the alkali metaphos-phate by precipitation or dialysis.
More specifically, the above described method is disclosed in U.S. Patent 2,377,624 wherein protein is re-covered in water soluble form from animal matter, as for example, whey, bovine serum and the like. The basic steps of this process comprise the addition of metaphosphoric acid or the equivalent amount of a water soluble metaphosphate, hexametaphosphate, or the like capable of yielding metaphosphoric acid; adjusting the pH within the range of 4.3 to 1.0, or preferably to about pH
3.0; separating the precipitated protein metaphosphate complex from the liquid; adding alkali to the precipitated protein metaphosphate complex to raise the pH to between about 6.0 and 12.0, preferably to about pH 9.0, to thereby disassociate the protein metaphosphate complex; and lastly the removal of meta-phosphate ions by means such as dialysis, or metaphosphate pre-cipitation.
More recently, U.S. Patent 3,637,543 disclosed that the protein-phosphate precipitate can be more easily recovered by initially substantially reducing or removing the divalent lOSS931 metal cations present in the proteinaceous solution by ion exchange, or selective precipitation of divalent metal cations by the addition of trisodium phosphate to the proteinaceous solution. The patent also teaches that the protein recovered from the redispersed alkali solution is made acid-soluble if the phosphate ion concentration is substantially reduced. The protein thus obtained can be used in acidic beverages.
However, none of the known processes yield acid-soluble protein exhibiting solution clarity at acid pH and therefore are not suitable for use in the fortification of acidic beverages requiring solution clarity. It has been found that although the known processes provide an acid-soluble protein.
the protein produces turbid solutions at acid pH. These turbid acidic protein solutions are not satisfactory for the forti-fication of acidic beverages which require protein solubility and solution clarity at acid pH.
Summary of the Invention According to the present invention, protein having improved solution clarity at acid pH is recovered from a proteinaceous aqueous solution by a process which comprises admixing with a proteinaceous aqueous solution a phosphate selected from the group consisting of tetrasodium pyrophosphate, tetra-potassium pyrophosphate, sodium acid pyrophosphate, potassium acid pyrophosphate, potassium tripolyphosphate, sodium tripoly-phosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, sodium iron pyrophosphate, ammonium pyrophosphate and mixtures thereof, at a concentration greater than 1.0 gram per liter to form a phosphate complexed solution; adjusting the pH of the phosphate complexed solution to a range of from about 6.0 to about 8.0 by the addition of a base to form a precipitate and a pretreated proteinaceous aqueous solution;
separating the precipitate from the pretreated proteinaceous aqueous solution; admixing the pretreated proteinaceous aqueous solution with a medium chain length polyphosphate of the formula:
O
X - O -- - P - O ---X
O
_ Y _ N ave.
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000 at a con-centration greater than 2.0 grams per liter to form a protein-phosphate complexed solution; adjusting the pH of the protein-phosphate complexed solution to a range of from about 4.5 to about 2.0 by the addition of acid to form a protein-phosphate precipitate and a supernatant solution; separating the protein-phosphate precipitate from the supernatant solution; dispersing the separated protein-phosphate precipitate in an aqueous solution having a final pH from about 5.0 to about 10.0; contacting the proteinphosphate dispersion with an anionic ion exchange resin to remove phosphate ions from the dispersion and provide a proteinaceous effluent; and recovering the proteinaceous effluent from the anionic ion exchange resin. The process provides a protein product exhibiting improved solution clarity at acid pH, which is useful in the protein fortification of acidic beverages.
~055931 Detailed Description of the Invention .
The proteinaceous solution of the present invention includes protein solutions derived from animal, vegetable or cellular materials. More specifically, the proteinaceous aqueous solution includes cheese wheyJ or soy whey. Preferably, the proteinaceous aqueous solution is cheese whey, or reconstituted dried cheese whey.
The term cheese whey is used herein to denote sweet cheese whey comprising cheddar cheese whey, Swiss cheese whey, mozzarella cheese whey, mixtures thereof and the like. Most preferably, the proteinaceous aqueous solution useful in the present invention is cheddar cheese whey, or reconstituted cheddar cheese whey.
The process of the present invention can be operated over a broad temperature range. Temperatures above the freezing point of the aqueous solution and below the point of substantial protein denaturation can be used. Preferably, the process of the present invention is operated at a temperature between about 40F. to about 130F. Most preferably, the process of the present invention is operated at a temperature between about 40F. to about 50F., or between about 120F. to about 130F.
in order to inhibit microbial growth during processing.
The proteinaceous aqueous solutions useful in the practice of the present invention contain dissolved protein at a concentration ranging from 2.0 grams per liter to about 100 grams per liter. The protein concentration in the aqueous solution is based on total Kjeldahl nitrogen. Protein is equal to total Kjeldahl nitrogen times the appropriate factor, for example, 6.38 in the case of milk protein and 6.25 in the case of vegetable protein determined in accordance with Methods of Analysis - A.O.A.C., 16 (1970), 11th Ed.
The initial step of the process of the present invention comprises admixing with the proteinaceous aqueous solution a phosphate pretreating agent selected from the group consisting of tetrasodium pyrophosphate, tetrapotassium pyro-phosphate, sodium acid pyrophosphate, potassium acid pyro-phosphate, potassium tripolyphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, sodium iron pyrophosphate, ammonium pyro-phosphate, and mixtures thereof.
The phosphate pretreating agent is admixed with the proteinaceous aqueous solution at a final pretreating agent solids concentration greater than 1.0 gram per liter to form a phosphate complexed solution. Preferably, the phosphate pre-treating agent of the present invention is admixed with the proteinaceous aqueous solution at a final pretreating agent solids concentration from about 3.5 grams per liter to about 4.5 grams per liter.
In addition, further improved results can be obtained by the addition of calcium chloride to the proteinaceous aqueous solution to give a final calcium chloride solids concentration from about 0.2 grams per liter to about 4.0 grams per liter. The calcium chloride can be added to the proteinaceous aqueous solution before, during, or after the addition of the phosphate I C~3512/3718 pretreating agent, but before the step of adjusting the pH to a range from about 6.0 to about 8Ø The phosphate pretreating agent of the present invention and, if added, the calcium chloride are dissolved in the proteinaceous aqueous solution by adequate stirring.
A base is added to the phosphate complexed solution.
The term base is used herein to denote alkaline reacting substances, for example, sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, and the like. The base is added to adjust the pH to a range of from about 6.0 to about 8Ø Preferably, a base is added to adjust the pH from about 7.0 to about 8Ø
The quantity of base added to the phosphate complexed solution depends upon the type of base being used.
When the base is added to the phosphate complexed solution a precipitate and a pretreated proteinaceous aqueous solution are formed. The precipitate contains reactants which if not removed at this time subsequently irreversibly combine with the protein to cause undesirable solution turbidity at acid pH. It has been found that the phosphate pretreating agent disclosed above must be added and the precipitate removed prior to the medium chain length polyphosphate addition step in order that the final product obtained by the process of the present invention exhibit solution clarity at acid pH.
The precipitate is separated from the pretreated proteinaceous aqueous solution to provide a separated precipitate and a separated pretreated proteinaceous aqueous solution. For example, the precipitate can be separated by centrifugal separation, by filtration, by settling or other means for separating solids from liquids. The separated pre-cipitate can be dried and used in food products as a substitute for nonfat milk solids.
` 1055931 . ,, ~; The separated pretreated proteinaceous aqueous solution is admixed with a medium chain length polyphosphate of ,` the formula:
~, O
''~ X - O _ p - O - X
_ _ N ave.
.~, Y
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000. Preferably, the medium chain length polyphosphate is of the type wherein N
ave. represents an average chain length from about 8 to about 14.
Most preferably, the medium chain length polyphosphate is of the type wherein N ave. represents an average chain length of about 10.3.
The medium chain length polyphosphates of the present invention is usually admixed with the separated pretreated proteinaceous aqueous solution at a concentration greater than
It is known that most food products can be nutritionally improved by protein fortification. Proteins heretofore useful for protein fortification include for example, soy protein, casein, and cheese whey proteins. Recently, it has become desirable to nutritionally improve acidic beverages by protein fortification. However, protein fortification of acidic beverages has been especially difficult, since proteins exhibit decreased solubility and increased solution turbidity at acid pH.
Recently, there has been particular interest in the use of proteins recovered from cheese whey for protein fortifi-cation of acidic beverages. This interest relates to the acid solubility of undenatured cheese whey proteins, which remain in solution at acid pH during the cheese making process.
In addition to protein solubilitv at acid pH, protein fortification of acidic beverages requires the maintenance of solution clarity at acid pH. Therefore, even though a particular protein exhibits adequate acid-solubility, the use thereof in acidic beverages is prohibited if the solution clarity at acid pH is unsatisfactory under the conditions of use.
Generally, it is known that protein can be recovered from proteinaceous aqueous solutions by the phosphate precipi-tation of protein from the proteinaceous aqueous solution and the recovered protein can be made acid-soluble by the subsequent removal of phosphate ions by conventional methods, e.g., anionic ion exchange, electrodialysis, and the like. Specifically, it is known that precipitation of protein can be effected from pro-tenaceous aqueous solutions by metaphosphoric acid addition at acid pH. The precipitated protein can then be resolubilized by n the disassociation of the protein metaphosphate complex by the addition of an alkali, and the removal of the alkali metaphos-phate by precipitation or dialysis.
More specifically, the above described method is disclosed in U.S. Patent 2,377,624 wherein protein is re-covered in water soluble form from animal matter, as for example, whey, bovine serum and the like. The basic steps of this process comprise the addition of metaphosphoric acid or the equivalent amount of a water soluble metaphosphate, hexametaphosphate, or the like capable of yielding metaphosphoric acid; adjusting the pH within the range of 4.3 to 1.0, or preferably to about pH
3.0; separating the precipitated protein metaphosphate complex from the liquid; adding alkali to the precipitated protein metaphosphate complex to raise the pH to between about 6.0 and 12.0, preferably to about pH 9.0, to thereby disassociate the protein metaphosphate complex; and lastly the removal of meta-phosphate ions by means such as dialysis, or metaphosphate pre-cipitation.
More recently, U.S. Patent 3,637,543 disclosed that the protein-phosphate precipitate can be more easily recovered by initially substantially reducing or removing the divalent lOSS931 metal cations present in the proteinaceous solution by ion exchange, or selective precipitation of divalent metal cations by the addition of trisodium phosphate to the proteinaceous solution. The patent also teaches that the protein recovered from the redispersed alkali solution is made acid-soluble if the phosphate ion concentration is substantially reduced. The protein thus obtained can be used in acidic beverages.
However, none of the known processes yield acid-soluble protein exhibiting solution clarity at acid pH and therefore are not suitable for use in the fortification of acidic beverages requiring solution clarity. It has been found that although the known processes provide an acid-soluble protein.
the protein produces turbid solutions at acid pH. These turbid acidic protein solutions are not satisfactory for the forti-fication of acidic beverages which require protein solubility and solution clarity at acid pH.
Summary of the Invention According to the present invention, protein having improved solution clarity at acid pH is recovered from a proteinaceous aqueous solution by a process which comprises admixing with a proteinaceous aqueous solution a phosphate selected from the group consisting of tetrasodium pyrophosphate, tetra-potassium pyrophosphate, sodium acid pyrophosphate, potassium acid pyrophosphate, potassium tripolyphosphate, sodium tripoly-phosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, sodium iron pyrophosphate, ammonium pyrophosphate and mixtures thereof, at a concentration greater than 1.0 gram per liter to form a phosphate complexed solution; adjusting the pH of the phosphate complexed solution to a range of from about 6.0 to about 8.0 by the addition of a base to form a precipitate and a pretreated proteinaceous aqueous solution;
separating the precipitate from the pretreated proteinaceous aqueous solution; admixing the pretreated proteinaceous aqueous solution with a medium chain length polyphosphate of the formula:
O
X - O -- - P - O ---X
O
_ Y _ N ave.
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000 at a con-centration greater than 2.0 grams per liter to form a protein-phosphate complexed solution; adjusting the pH of the protein-phosphate complexed solution to a range of from about 4.5 to about 2.0 by the addition of acid to form a protein-phosphate precipitate and a supernatant solution; separating the protein-phosphate precipitate from the supernatant solution; dispersing the separated protein-phosphate precipitate in an aqueous solution having a final pH from about 5.0 to about 10.0; contacting the proteinphosphate dispersion with an anionic ion exchange resin to remove phosphate ions from the dispersion and provide a proteinaceous effluent; and recovering the proteinaceous effluent from the anionic ion exchange resin. The process provides a protein product exhibiting improved solution clarity at acid pH, which is useful in the protein fortification of acidic beverages.
~055931 Detailed Description of the Invention .
The proteinaceous solution of the present invention includes protein solutions derived from animal, vegetable or cellular materials. More specifically, the proteinaceous aqueous solution includes cheese wheyJ or soy whey. Preferably, the proteinaceous aqueous solution is cheese whey, or reconstituted dried cheese whey.
The term cheese whey is used herein to denote sweet cheese whey comprising cheddar cheese whey, Swiss cheese whey, mozzarella cheese whey, mixtures thereof and the like. Most preferably, the proteinaceous aqueous solution useful in the present invention is cheddar cheese whey, or reconstituted cheddar cheese whey.
The process of the present invention can be operated over a broad temperature range. Temperatures above the freezing point of the aqueous solution and below the point of substantial protein denaturation can be used. Preferably, the process of the present invention is operated at a temperature between about 40F. to about 130F. Most preferably, the process of the present invention is operated at a temperature between about 40F. to about 50F., or between about 120F. to about 130F.
in order to inhibit microbial growth during processing.
The proteinaceous aqueous solutions useful in the practice of the present invention contain dissolved protein at a concentration ranging from 2.0 grams per liter to about 100 grams per liter. The protein concentration in the aqueous solution is based on total Kjeldahl nitrogen. Protein is equal to total Kjeldahl nitrogen times the appropriate factor, for example, 6.38 in the case of milk protein and 6.25 in the case of vegetable protein determined in accordance with Methods of Analysis - A.O.A.C., 16 (1970), 11th Ed.
The initial step of the process of the present invention comprises admixing with the proteinaceous aqueous solution a phosphate pretreating agent selected from the group consisting of tetrasodium pyrophosphate, tetrapotassium pyro-phosphate, sodium acid pyrophosphate, potassium acid pyro-phosphate, potassium tripolyphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, sodium iron pyrophosphate, ammonium pyro-phosphate, and mixtures thereof.
The phosphate pretreating agent is admixed with the proteinaceous aqueous solution at a final pretreating agent solids concentration greater than 1.0 gram per liter to form a phosphate complexed solution. Preferably, the phosphate pre-treating agent of the present invention is admixed with the proteinaceous aqueous solution at a final pretreating agent solids concentration from about 3.5 grams per liter to about 4.5 grams per liter.
In addition, further improved results can be obtained by the addition of calcium chloride to the proteinaceous aqueous solution to give a final calcium chloride solids concentration from about 0.2 grams per liter to about 4.0 grams per liter. The calcium chloride can be added to the proteinaceous aqueous solution before, during, or after the addition of the phosphate I C~3512/3718 pretreating agent, but before the step of adjusting the pH to a range from about 6.0 to about 8Ø The phosphate pretreating agent of the present invention and, if added, the calcium chloride are dissolved in the proteinaceous aqueous solution by adequate stirring.
A base is added to the phosphate complexed solution.
The term base is used herein to denote alkaline reacting substances, for example, sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, and the like. The base is added to adjust the pH to a range of from about 6.0 to about 8Ø Preferably, a base is added to adjust the pH from about 7.0 to about 8Ø
The quantity of base added to the phosphate complexed solution depends upon the type of base being used.
When the base is added to the phosphate complexed solution a precipitate and a pretreated proteinaceous aqueous solution are formed. The precipitate contains reactants which if not removed at this time subsequently irreversibly combine with the protein to cause undesirable solution turbidity at acid pH. It has been found that the phosphate pretreating agent disclosed above must be added and the precipitate removed prior to the medium chain length polyphosphate addition step in order that the final product obtained by the process of the present invention exhibit solution clarity at acid pH.
The precipitate is separated from the pretreated proteinaceous aqueous solution to provide a separated precipitate and a separated pretreated proteinaceous aqueous solution. For example, the precipitate can be separated by centrifugal separation, by filtration, by settling or other means for separating solids from liquids. The separated pre-cipitate can be dried and used in food products as a substitute for nonfat milk solids.
` 1055931 . ,, ~; The separated pretreated proteinaceous aqueous solution is admixed with a medium chain length polyphosphate of ,` the formula:
~, O
''~ X - O _ p - O - X
_ _ N ave.
.~, Y
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000. Preferably, the medium chain length polyphosphate is of the type wherein N
ave. represents an average chain length from about 8 to about 14.
Most preferably, the medium chain length polyphosphate is of the type wherein N ave. represents an average chain length of about 10.3.
The medium chain length polyphosphates of the present invention is usually admixed with the separated pretreated proteinaceous aqueous solution at a concentration greater than
2.0 grams per liter. Preferably, medium chain length polyphosphates of the present invention are admixed with the separated pre-treated proteinaceous aqueous solution at a concentration from about 5.0 grams per liter to about 10 grams per liter.
Also, the admixture of the medium chain length polyphos-phate and the separated pretreated proteinaceous aqueous solution is preferably accompanied by stirring in order to insure sufficient solubilization of the added medium chain length polyphosphate.
Stirring can be accomplished by any effective means, as for ~ 1055931 example, air injection or mechanical stirring means.
Admixing the medium chain length polyphosphate with the separated pretreated proteinaceous aqueous solution in accordance with the present invention forms a protein-phosphate complexed solution. The pH of the protein-phosphate complexed solution is adjusted by the addition of an acid to a pH in a range of from about 4.5 to about 2Ø Preferably, the acid is added in an amount to adjust the pH to a ranae of from about
Also, the admixture of the medium chain length polyphos-phate and the separated pretreated proteinaceous aqueous solution is preferably accompanied by stirring in order to insure sufficient solubilization of the added medium chain length polyphosphate.
Stirring can be accomplished by any effective means, as for ~ 1055931 example, air injection or mechanical stirring means.
Admixing the medium chain length polyphosphate with the separated pretreated proteinaceous aqueous solution in accordance with the present invention forms a protein-phosphate complexed solution. The pH of the protein-phosphate complexed solution is adjusted by the addition of an acid to a pH in a range of from about 4.5 to about 2Ø Preferably, the acid is added in an amount to adjust the pH to a ranae of from about
3.0 to about 4Ø
The term acid is used herein to denote acidic reacting substances, for example, mineral, or organic acids. Specifically, mineral acids such as hydrochloric acid, sulfuric acid, phos-phoric acid, or ~r~a~ic acids such as lactic acid, citric acid, mixtures thereof, and the like can be used herein. Preferably, food grade hydrochloric acid or phosphoric acid is used in the process of the present invention.
~qhen the pH of the protein-phosphate complexed sol-ution is adjusted to a range of from about 4.5 to about 2.0 a protein-phosphate precipitate and a supernatant solution are formed. The protein-phosphate precipitate forms rapidly upon pH adjustment; however, a hold time of at least 10 minutes at the acid pH range is preferred to provide sufficient time for complete protein-phosphate precipitate formation.
The protein-phosphate precipitate is separated from the supernatant solution by conventional means. For example, the protein-phosphate precipitate can be separated from the supernatant solution by centrifugal separation, by filtration, by settling or other means for separating solids from liquids.
The protein concentration of the protein-phosphate precipitate can range from about 50% to about 80~ (dry solids basis).
Preferably, the protein content of the protein-phosphate precipitate is from about 55~ to about 70~ (dry solids basis).
1055~31 The phosphate concentration of the protein-phosphate precipitate can range from about 5% to about 25% (dry solids basis). Pre-ferably, the phosphate concentration of the protein-phosphate , precipitate is from about 10% to about 20% (dry solids basis).
The separated protein-phosphate precipitate is dis-persed by adding the precipitate to water and maintaining the pH in the range of from about 5.0 to about 12.0, preferably in the range from about 5.0 to about 8.0 to thereby form a protein-phosphate dispersion. Preferably, the protein-phosphate preci-pitate is dispersed by stirring. Dispersion of the protein-phosphate precipitate occurs within about 10 to about 30 minutes.
The protein-phosphate precipitate can be dispersed at a solids concentration from about 10 grams per liter to about 500 grams per liter. Preferably, the protein-phosphate precipitate is dispersed at a solids concentration from about 30 grams per liter to about 70 grams per liter.
The phosphate is separated from the protein-phosphate dispersion by contacting the protein-phosphate dispersion with an anionic ion exchange resin to remove phosphate ions and provide a proteinaceous effluent. The solids concentration of the protein-phosphate dispersion is maintained from about 10 grams per liter to about 100 grams per liter. Preferably, the solids content of the protein-phosphate dispersion is maintained from about 40 grams per liter to about 60 grams per liter.
By anionic ion exchange resin, it is meant herein, anion ion exchange resins capable of substantially exchanging the polyphosphate anions contained in the protein-phosphate dis-persion. More specifically, the following commercially available anionic ion exchange resins are useful; Dowex lXl, Dowex lX2, * * * *
Dowex lX4, AMBERLITE IRA 401, and Duolite A-102D. Duolite A-102D
*Trademark is preferred, since this anionic exchange resin has the greatest capacity for polyphosphate anions, i.e., 1.0 to 1.1 milli equivalent polyphosphate per milliliter of resin [rJitschmann, Hs., Rickli E., and Kistler, P., Vox Sang., Volume 5, pages 232-252 (1960)].
Conventional anionic ion exchange removal of polyphos-phate anions is preferably accomplished as follows. A column containing an anionic ion exchange resin of the type described above is prepared in a conventional manner. Column preparation involves placing the resin in a column having desired dimensions.
The fresh resin is then washed, usually with deionized or distilled water.
The protein-phosphate dispersion can be passed through the anionic ion exchange resin at an appropriate effluent flow rate until the ion exchange capacity of the resin is exhausted.
The exhausted resin can be regenerated by sequentially washing:
with dilute base; with water to a pH between about 8 to 9;
with a large volume of dilute solution of sodium chloride and finally with water. Immediately after resin regeneration, the resin may again be used to remove phosphate anions from the protein-phosphate dispersion.
The proteinaceous effluent can be dried by spray dry-ing, vacuum drying, freeze drying or other drying methods commonly used to dry proteinaceous solutions. Also the proteinaceous effluent can be concentrated by vacuum evaporative methods or other known methods commonly used to concentrate proteinaceous solutions to provide a protein concentrate. The protein concentrate can then be dried in accordance with the conventional methods.
The proteinaceous effluent exhibits solubility and unexpected solution clarity at acid pH, and can be used to fortify acidic beverages and particularly clear acidic beverages.
~ 12 -~055931 The use of the protein of the present invention in the forti-fication of acidic beverages is desirable in terms of providing substantial increased nutritional benefit without adversely affecting beverage clarity or flavor.
The protein obtained in accordance with the process ; of the present invention can be used in acidic beverages at a protein concentration between about 2.0 grams per liter to about 30 grams per liter. Preferably, the protein of the present invention is used i-n acidic beverages at a protein concentration between about 10 grams per liter to about 20 grams per liter.
The process of the present invention is further illus-trated in the examples set forth below.
To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed sodium acid pyrophosphate at a concentration of 40 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was then adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate formed upon base addition was sep-arated from the pretreated cheese whey solution by gravity filtration through number 541 Whatman Filter Paper to give a separated precipitate and a separated pretreated cheese whey solution. To the separated pretreated cheese whey solution was admixed sodium polyphosphate (N ave. = 10.3) at a con-centration of 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate complexed solution was stirred and the pH adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatantsolution. The protein-phosphate pr~cipitate was separated from the supernatant solution by gravity filtration through number 541 Whatman Filter Paper. The separated protein-* Trademark phosphate precipitate was dispersed by stirring the precipitate in 50 milliliters of water having a pH of 7.5 to form a protein-phosphate dispersion. The protein-phosphate dispersion was contacted with an anionic ion exchange resin, commercially available under under the tradename DUOLITE A-102D from Diamond Shamrock Chemical Co., to provide a whey protein effluent. The ion exchange column was 22 centimeters high and 1.5 centimeters in diameter and contained 28.4 grams of the dry ~ resin. The anionic ion exchange resin was in the chloride form.
The total volume of feed material was contacted with the ion exchange resin and the whey protein effluent collected at a flow rate of 36 ml./hr./cm2. The whey protein effluent was dried by freeze drying. The dried sample was used for further testing.
The freeze dried sample was assayed for protein in accordance with conventional methods (% N x 6.38): Methods of Analysis - A.O.A.C., 16, (1970) 11th Ed. The protein concen-tration of the freeze dried sample was 66.7% (dry solids basis) and is shown in Table I. The solution clarity of the freeze dried sample was determined by first redissolving the freeze dried sample at a protein concentration of 10 grams per liter and adjusting the pH to 3.0 by the addition of acid. The light transmittance of the solution was determined at 625 milli-microns on a Beckman DBG spectrophotometer. The light trans-mittance of the solution was 71.0% and is shown in Table I.
To a 100 milliliters of defatted cheddar cheese whey was admixed a sodium polyphosphate (N ave. = 10.3) at a con-centration of 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate solution was there-after treated as described in Example 1 by dispersing the lOS593~
the precipitate in water, contacting the dispersion with the anionic ion exchange resin, and recovering the whey protein effluent. The freeze dried sample was assayed for protein as described in Example 1 and the results shown in Table I. The light transmittance of this sample, determined as described in Example 1, was 0.9% and is presented in Table I.
It is apparent from the data shown in Table I relating to Examples 1 and 2 that a substantial increase in solution clarity at acid pH is obtained by treating cheddar cheese whey in accordance with the process of the present invention.
To 100 milliliters of defatted cheddar cheese whey having an initial pH of 6.1 was admixed sodium acid pyrophosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 1.2 grams per liter, as 1.5 milliliters of an 80 grams per liter stock sol-ution. The pR of the phosphate complexed solution was adjusted to 7.04 by the addition of sodium hydroxide to form a precipi-tate and a pretreated cheese whey solution. The remaining steps were as those described in Example 1.
A protein solution having a protein concentration of 10 grams per liter and a pH of 3.0 was prepared in accordance with Example 1. The light transmittance of this protein sol-ution was 77.3% and is presented in Table I.
It is clear from Examples 2 and 3 in Table I that pre-treatment in accordance with the present invention by calcium chloride solution addition provides an increase in the solution clarity of the whey protein solution at pH 3Ø
._ 15_ ~ C-3512/3718 , To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was adjusted-to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The remaining steps were as described in Example 1.
The freeze dried cheese whey protein was dissolved in water at a protein concentration of 10 grams per liter. The pH was then adjusted to 3.0 as previously described in Example 1.
The light transmittance at 625 millimicrons of the protein solution, determined as previously described, was 43.2% and is shown in Table I.
E~MPLE 5 To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 1.2 grams per liter, as 1.5 milliliters of an 80 grams per liter stock sol-ution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The remaining steps were as described in Example 1.
The freeze dried protein was dissolved in water at a protein concentration of 10 grams per liter. The pH was then 105593~
adjusted to 3.0 as previously described. The light transmittance of this solution was 71.9% as determined in accordance with the method described in Example 1 and is shown in Table I.
To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 there was admixed tetrasodium pyrophosphate at a concentration at 4.5 grams per liter, as 15 milliliters of a 30 grams per liter stock solution, to thereby form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concen-tration of 2.8 grams per liter, as 3.5 milliliters of a 80 grams per liter stock solution. The pH of the phosphate complexed solution was adjusted to 7.07 by the addition of sodium hydroxide. The remaining steps were as described in Example 1.
The light transmittance of a solution of the freeze dried protein was determined by dissolving the dried protein in water at a protein concentration of 10 grams per liter. The pH was then adjusted to about 3.0 by the addition of acid.
The light transmittance of whey protein solution was 69.7~ and is shown in Table I.
It is clear from Examples 2, 4, 5J and 6 in Table I
that pretreatment with the phosphates of the present invention are effective in terms of providing protein solutions exhibiting improved solution clarity at pH 3Ø
~055931 o q) o ~
U ~ o ~ U~rl 1~ rl ~) O C5~ ~N 0~ t`
~ rl ~ 'I O 1`
rl ~1 0 1~ ~ ~ 1~ U~
.~ o rl ~ O
dP
P~
O lQ
~-rl ~q ~1 O
O
O i~
.' d~
H N
~ C~ ~
,. N
N
o u~
O ~: O
Z N .C ~ ~
S~ 0 'J ~ S~
.. .. ~ U~ tO
a) o a~
o oo o o a a~
S~ O
æl = ~ E~
~1 rl N 11~
X
Examples 7-10 show the effect of substantially lower phosphate pretreating agent concentrations on the solution clarity of the whey protein solutions prepared in accordance with the procedures previously described at pH 6.0 and at pH
3Ø
To 100 milliliters of cheddar cheese whey obtained by reconstituting 6.5 grams of commercially available spray dried cheddar cheese whey in 100 milliliters of water, was admixed potassium tripolyphosphate at a concentration of 1.0 gram per liter, as 1.25 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate was separated from the second cheese whey solution by gravity filtration through a number 541 Whatman Filter Paper to give a separated precipitate and a separated pretreated cheese whey solution.
To the separated pretreated cheese whey solution, there was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of about 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate complexed solution was stirred and the pH adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatant so-lution. The protein-phosphate precipitate was separated from the supernatant solution by centrifugation at 2500 rpm in an International Centrifuge for 25 minutes. The remaining steps were as described in Example I.
C=3512/3718 lOSS931 The whey protein effluent was freeze dried as previously described in Example 1. The freeze dried whey protein was dis-solved i~ water at a protein concentration of 10 grams per liter.
The pH of the whey protein solution was adjusted to 6.0 by the addition of hydrochloric acid. The solution clarity of the solution at pH 6.0 was determined, as previously described, by measuring the percent light transmittance of the whey protein solution, and is presented in Table II.
The pH of the whey protein solution was adjusted to 3.0 as described in Example 1. The percent light transmittance of the whey protein solution at 625 millimicrons was 11.5%
determined as previously described in Example 1 and is shown in Table II.
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of 10 grams per liter to form a protein-phosphate solution. The protein-phosphate solu-tion was thereafter treated as described in Example 7. The whey protein effluent was freeze dried. The freeze dried whey protein was dissolved in water at a protein concentration of 10 grams per liter. The pH of the whey protein solution was adjusted to 6.0 and the solution clarity determined as described in Example 7, and is presented in Table II. The pH was then adjusted to 3.0 as described in Example 1. The solution clarity of the whey protein solution at pH 3.0 as indicated by the percent transmittance at 625 millimicrons was 0, determined as previously described in Example 1 and is shown in Table II.
It is clear from Examples 7 and 8 in Table II that pretreatment with the phosphate pretreating agent at a sub-stantially reduced concentration provides a protein solution with improved solution clarity at pH 3Ø
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, having a pH of 6.0, was admixed potassium tripolyphosphate at a concentration of 1.0 gram per liter, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 0.3 grams per liter, as 0.375 milliliters of an 80 grams per liter stock solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide. The phosphate complexed solution was treated as described in Example 7. The solution clarity of the whey protein solution at pH 6.0 and pH 3.0, as indicated by percent trans-mittance at 625 millimicrons, were 8.3 and 18.0, respectively.
The solution clarities of the whey protein solutions were determined as previously described in Example 1 and are presented in Table II. It is clear from Examples 7 and 9 that improved solution clarity is obtained at both pH 6.0 and pH 3.0 by the optional addition of calcium chloride to the phosphate complexed solution.
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 millimeters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The remaining steps were as those described in Example 7.
The solution clarity of the whey protein solution at pH 6.0 and pH 3.0, as indicated by the percent transmittance at 625 millimicrons, were 64.5% and 66.2%, respectively. The solution clarities of the whey solutions were determined as previously described in E~xample 1 and are presented in Table II. It is clear from Examples 7, 8, and 9 of Table II that substantially improved results are obtained with the phosphate pretreating agent concentrations in the range of 4.0 grams per liter.
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; C-3512/3718 Examples 11-13 show the effect of phosphate removal on the protein concentration, phosphorus concentration, and the sol-ution clarity at pH 3.0 of the whey protein obtained in accor-dance with the present invention (Examples 11 and 13) compared to the control samples (Example 12).
To 700 milliliters of defatted cheese whey at a tem-perature of 125F. was admixed sodium acid pyrophosphate at a concentration of 4.0 grams per liter, as 35 milliliters of 80 grams per liter stock solution, to form a phosphate complexèd solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate was separated from the pretreated cheese whey solution by gravity lS filtration as previously described in ~xample 1 to give a separated precipitate and a separated pretreated cheese whey solution.
To the separated second cheese whey solution, heated to 125F., was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of 9.0 grams per liter to form a protein-phosphate complexed solution. The pH of the protein-phosphate complexed solution was adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatant solution.
The protein-phosphate precipitate was separated from the supernatant solution by filtration through number 541 Whatman Filter Paper. The separated protein-phosphate precipitate was dispersed in 100 milliliters of water by stirring the separated protein-phosphate precipitate in the water having a pH of 7.0 to form a protein-phosphate dispersion. 50 milliliters of the protein-phosphate dispersion was passed through an anionic ion exchange resin and freeze dried as described in Example 1.
The remaining 50 milliliters of the protein-phosphate dispersion was freeze dried without phosphate removal.
The protein concentrations of the treated whey protein product (phosphate removed) and the untreated whey protein product were determined in accordance with: Methods of Analysis, A.O.A.C., 16, tl970) 11th Ed., and are presented in Table III.
Also, the phosphorus concentration of the treated whey protein product and the untreated whey protein product were determined in accordance with Method of Analysis- A.O.A.C., 2.016, (1965) 10th Ed. and are presented in Table III.
The freeze dried treated whey protein and the untreated whey protein product were dissolved in water at a protein con-centration of 10 grams per liter. The pH of the whey protein solutions were adjusted to 3.0 as previously described in Example 1. The solution clarities of the whey protein solutions at pH 3.0, as indicated by percent light transmittance, at 625 millimicrons, were 38.8%, for the treated whey protein product and not calculable for the untreated whey protein product. The solution clarities were determined as previously described in Example 1, and are shown in Table III.
To 390 milliliters of defatted cheddar cheese whey obtained as described in Example 11, at a temperature of 125F., sodium polyphosphate (N ave. = 10.3) at a concentration of 9.0 grams per liter to form a protein-phosphate complexed solution.
The protein-phosphate complexed solution was thereafter treated as described in Example 11. The protein concentrations, and phosphate concentrations of the treated and untreated whey protein products were determined as described in Example 11, and are presented in Table III. The solution clarities of the whey protein solutions, i.e., treated and untreated, at pH 3.0, as indicated by the percent transmittance at 625 millimicrons were 1.3~, (treated), and not calculable (untreated) determined as previously described in Example 1, and are shown in Table III.
C-3~12/3718 It is clear from Examples 11 and 12 that pretreatment of cheese whey by the addition of the phosphate combined with phosphate removal provides whey protein products with increased protein concentration, reduced phosphate concentration, and substantially improved solution clarity at acid pH ~pH 3.0).
Example 13 shows the effect of pretreatment by the addition of the phosphate pretreating agent and the calcium chloride to provide improved results.
To 700 milliliters of defatted cheddar cheese whey at a temperature of 125F. was admixed sodium acid pyrophos-phate at a concentration of 4.0 grams per liter, as 35 milli-liters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a con-centration of 1.14 grams per liter, as 10 milliliters of an 80 grams per liter stock solution. The pH of the phosphate complexed solution was ad]usted to 7.0 by the addition of sodium hydroxide. The phosphate complexed solution was thereafter treated as described in Example 11.
The separated protein-phosphate precipitate was d~is-persed in 250 milliliters of water by stirring the separated protein-phosphate precipitate in the water having a pH of about 7.0 to form a protein-phosphate dispersion. 125 milliliters of the protein-phosphate dispersion were passed through an anionic ion exchange resin and the effluent freeze dried, as previously described in Example 1.
The protein and phosphate concentrations of the treated and untreated whey protein products were determined as previously described in Example 11, and are presented in Table III. The freeze dried, treated and untreated, whey protein were products dissolved in water at a protein concentration of 10 grams per liter. The pH was adjusted to 3.0 as previously described in Example 1. The solution clarities of the whey protein solutions at pH 3.0, as indicated by the percent light transmittance at 625 millimicrons were 77.3~, (treated) and not calcuable (untreated) determined as previously described in Example 1, and are disclosed in Table III.
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The term acid is used herein to denote acidic reacting substances, for example, mineral, or organic acids. Specifically, mineral acids such as hydrochloric acid, sulfuric acid, phos-phoric acid, or ~r~a~ic acids such as lactic acid, citric acid, mixtures thereof, and the like can be used herein. Preferably, food grade hydrochloric acid or phosphoric acid is used in the process of the present invention.
~qhen the pH of the protein-phosphate complexed sol-ution is adjusted to a range of from about 4.5 to about 2.0 a protein-phosphate precipitate and a supernatant solution are formed. The protein-phosphate precipitate forms rapidly upon pH adjustment; however, a hold time of at least 10 minutes at the acid pH range is preferred to provide sufficient time for complete protein-phosphate precipitate formation.
The protein-phosphate precipitate is separated from the supernatant solution by conventional means. For example, the protein-phosphate precipitate can be separated from the supernatant solution by centrifugal separation, by filtration, by settling or other means for separating solids from liquids.
The protein concentration of the protein-phosphate precipitate can range from about 50% to about 80~ (dry solids basis).
Preferably, the protein content of the protein-phosphate precipitate is from about 55~ to about 70~ (dry solids basis).
1055~31 The phosphate concentration of the protein-phosphate precipitate can range from about 5% to about 25% (dry solids basis). Pre-ferably, the phosphate concentration of the protein-phosphate , precipitate is from about 10% to about 20% (dry solids basis).
The separated protein-phosphate precipitate is dis-persed by adding the precipitate to water and maintaining the pH in the range of from about 5.0 to about 12.0, preferably in the range from about 5.0 to about 8.0 to thereby form a protein-phosphate dispersion. Preferably, the protein-phosphate preci-pitate is dispersed by stirring. Dispersion of the protein-phosphate precipitate occurs within about 10 to about 30 minutes.
The protein-phosphate precipitate can be dispersed at a solids concentration from about 10 grams per liter to about 500 grams per liter. Preferably, the protein-phosphate precipitate is dispersed at a solids concentration from about 30 grams per liter to about 70 grams per liter.
The phosphate is separated from the protein-phosphate dispersion by contacting the protein-phosphate dispersion with an anionic ion exchange resin to remove phosphate ions and provide a proteinaceous effluent. The solids concentration of the protein-phosphate dispersion is maintained from about 10 grams per liter to about 100 grams per liter. Preferably, the solids content of the protein-phosphate dispersion is maintained from about 40 grams per liter to about 60 grams per liter.
By anionic ion exchange resin, it is meant herein, anion ion exchange resins capable of substantially exchanging the polyphosphate anions contained in the protein-phosphate dis-persion. More specifically, the following commercially available anionic ion exchange resins are useful; Dowex lXl, Dowex lX2, * * * *
Dowex lX4, AMBERLITE IRA 401, and Duolite A-102D. Duolite A-102D
*Trademark is preferred, since this anionic exchange resin has the greatest capacity for polyphosphate anions, i.e., 1.0 to 1.1 milli equivalent polyphosphate per milliliter of resin [rJitschmann, Hs., Rickli E., and Kistler, P., Vox Sang., Volume 5, pages 232-252 (1960)].
Conventional anionic ion exchange removal of polyphos-phate anions is preferably accomplished as follows. A column containing an anionic ion exchange resin of the type described above is prepared in a conventional manner. Column preparation involves placing the resin in a column having desired dimensions.
The fresh resin is then washed, usually with deionized or distilled water.
The protein-phosphate dispersion can be passed through the anionic ion exchange resin at an appropriate effluent flow rate until the ion exchange capacity of the resin is exhausted.
The exhausted resin can be regenerated by sequentially washing:
with dilute base; with water to a pH between about 8 to 9;
with a large volume of dilute solution of sodium chloride and finally with water. Immediately after resin regeneration, the resin may again be used to remove phosphate anions from the protein-phosphate dispersion.
The proteinaceous effluent can be dried by spray dry-ing, vacuum drying, freeze drying or other drying methods commonly used to dry proteinaceous solutions. Also the proteinaceous effluent can be concentrated by vacuum evaporative methods or other known methods commonly used to concentrate proteinaceous solutions to provide a protein concentrate. The protein concentrate can then be dried in accordance with the conventional methods.
The proteinaceous effluent exhibits solubility and unexpected solution clarity at acid pH, and can be used to fortify acidic beverages and particularly clear acidic beverages.
~ 12 -~055931 The use of the protein of the present invention in the forti-fication of acidic beverages is desirable in terms of providing substantial increased nutritional benefit without adversely affecting beverage clarity or flavor.
The protein obtained in accordance with the process ; of the present invention can be used in acidic beverages at a protein concentration between about 2.0 grams per liter to about 30 grams per liter. Preferably, the protein of the present invention is used i-n acidic beverages at a protein concentration between about 10 grams per liter to about 20 grams per liter.
The process of the present invention is further illus-trated in the examples set forth below.
To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed sodium acid pyrophosphate at a concentration of 40 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was then adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate formed upon base addition was sep-arated from the pretreated cheese whey solution by gravity filtration through number 541 Whatman Filter Paper to give a separated precipitate and a separated pretreated cheese whey solution. To the separated pretreated cheese whey solution was admixed sodium polyphosphate (N ave. = 10.3) at a con-centration of 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate complexed solution was stirred and the pH adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatantsolution. The protein-phosphate pr~cipitate was separated from the supernatant solution by gravity filtration through number 541 Whatman Filter Paper. The separated protein-* Trademark phosphate precipitate was dispersed by stirring the precipitate in 50 milliliters of water having a pH of 7.5 to form a protein-phosphate dispersion. The protein-phosphate dispersion was contacted with an anionic ion exchange resin, commercially available under under the tradename DUOLITE A-102D from Diamond Shamrock Chemical Co., to provide a whey protein effluent. The ion exchange column was 22 centimeters high and 1.5 centimeters in diameter and contained 28.4 grams of the dry ~ resin. The anionic ion exchange resin was in the chloride form.
The total volume of feed material was contacted with the ion exchange resin and the whey protein effluent collected at a flow rate of 36 ml./hr./cm2. The whey protein effluent was dried by freeze drying. The dried sample was used for further testing.
The freeze dried sample was assayed for protein in accordance with conventional methods (% N x 6.38): Methods of Analysis - A.O.A.C., 16, (1970) 11th Ed. The protein concen-tration of the freeze dried sample was 66.7% (dry solids basis) and is shown in Table I. The solution clarity of the freeze dried sample was determined by first redissolving the freeze dried sample at a protein concentration of 10 grams per liter and adjusting the pH to 3.0 by the addition of acid. The light transmittance of the solution was determined at 625 milli-microns on a Beckman DBG spectrophotometer. The light trans-mittance of the solution was 71.0% and is shown in Table I.
To a 100 milliliters of defatted cheddar cheese whey was admixed a sodium polyphosphate (N ave. = 10.3) at a con-centration of 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate solution was there-after treated as described in Example 1 by dispersing the lOS593~
the precipitate in water, contacting the dispersion with the anionic ion exchange resin, and recovering the whey protein effluent. The freeze dried sample was assayed for protein as described in Example 1 and the results shown in Table I. The light transmittance of this sample, determined as described in Example 1, was 0.9% and is presented in Table I.
It is apparent from the data shown in Table I relating to Examples 1 and 2 that a substantial increase in solution clarity at acid pH is obtained by treating cheddar cheese whey in accordance with the process of the present invention.
To 100 milliliters of defatted cheddar cheese whey having an initial pH of 6.1 was admixed sodium acid pyrophosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 1.2 grams per liter, as 1.5 milliliters of an 80 grams per liter stock sol-ution. The pR of the phosphate complexed solution was adjusted to 7.04 by the addition of sodium hydroxide to form a precipi-tate and a pretreated cheese whey solution. The remaining steps were as those described in Example 1.
A protein solution having a protein concentration of 10 grams per liter and a pH of 3.0 was prepared in accordance with Example 1. The light transmittance of this protein sol-ution was 77.3% and is presented in Table I.
It is clear from Examples 2 and 3 in Table I that pre-treatment in accordance with the present invention by calcium chloride solution addition provides an increase in the solution clarity of the whey protein solution at pH 3Ø
._ 15_ ~ C-3512/3718 , To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was adjusted-to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The remaining steps were as described in Example 1.
The freeze dried cheese whey protein was dissolved in water at a protein concentration of 10 grams per liter. The pH was then adjusted to 3.0 as previously described in Example 1.
The light transmittance at 625 millimicrons of the protein solution, determined as previously described, was 43.2% and is shown in Table I.
E~MPLE 5 To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 1.2 grams per liter, as 1.5 milliliters of an 80 grams per liter stock sol-ution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The remaining steps were as described in Example 1.
The freeze dried protein was dissolved in water at a protein concentration of 10 grams per liter. The pH was then 105593~
adjusted to 3.0 as previously described. The light transmittance of this solution was 71.9% as determined in accordance with the method described in Example 1 and is shown in Table I.
To 100 milliliters of defatted cheddar cheese whey having a pH of 6.0 there was admixed tetrasodium pyrophosphate at a concentration at 4.5 grams per liter, as 15 milliliters of a 30 grams per liter stock solution, to thereby form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concen-tration of 2.8 grams per liter, as 3.5 milliliters of a 80 grams per liter stock solution. The pH of the phosphate complexed solution was adjusted to 7.07 by the addition of sodium hydroxide. The remaining steps were as described in Example 1.
The light transmittance of a solution of the freeze dried protein was determined by dissolving the dried protein in water at a protein concentration of 10 grams per liter. The pH was then adjusted to about 3.0 by the addition of acid.
The light transmittance of whey protein solution was 69.7~ and is shown in Table I.
It is clear from Examples 2, 4, 5J and 6 in Table I
that pretreatment with the phosphates of the present invention are effective in terms of providing protein solutions exhibiting improved solution clarity at pH 3Ø
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Examples 7-10 show the effect of substantially lower phosphate pretreating agent concentrations on the solution clarity of the whey protein solutions prepared in accordance with the procedures previously described at pH 6.0 and at pH
3Ø
To 100 milliliters of cheddar cheese whey obtained by reconstituting 6.5 grams of commercially available spray dried cheddar cheese whey in 100 milliliters of water, was admixed potassium tripolyphosphate at a concentration of 1.0 gram per liter, as 1.25 milliliters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate was separated from the second cheese whey solution by gravity filtration through a number 541 Whatman Filter Paper to give a separated precipitate and a separated pretreated cheese whey solution.
To the separated pretreated cheese whey solution, there was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of about 10 grams per liter to form a protein-phosphate complexed solution. The protein-phosphate complexed solution was stirred and the pH adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatant so-lution. The protein-phosphate precipitate was separated from the supernatant solution by centrifugation at 2500 rpm in an International Centrifuge for 25 minutes. The remaining steps were as described in Example I.
C=3512/3718 lOSS931 The whey protein effluent was freeze dried as previously described in Example 1. The freeze dried whey protein was dis-solved i~ water at a protein concentration of 10 grams per liter.
The pH of the whey protein solution was adjusted to 6.0 by the addition of hydrochloric acid. The solution clarity of the solution at pH 6.0 was determined, as previously described, by measuring the percent light transmittance of the whey protein solution, and is presented in Table II.
The pH of the whey protein solution was adjusted to 3.0 as described in Example 1. The percent light transmittance of the whey protein solution at 625 millimicrons was 11.5%
determined as previously described in Example 1 and is shown in Table II.
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of 10 grams per liter to form a protein-phosphate solution. The protein-phosphate solu-tion was thereafter treated as described in Example 7. The whey protein effluent was freeze dried. The freeze dried whey protein was dissolved in water at a protein concentration of 10 grams per liter. The pH of the whey protein solution was adjusted to 6.0 and the solution clarity determined as described in Example 7, and is presented in Table II. The pH was then adjusted to 3.0 as described in Example 1. The solution clarity of the whey protein solution at pH 3.0 as indicated by the percent transmittance at 625 millimicrons was 0, determined as previously described in Example 1 and is shown in Table II.
It is clear from Examples 7 and 8 in Table II that pretreatment with the phosphate pretreating agent at a sub-stantially reduced concentration provides a protein solution with improved solution clarity at pH 3Ø
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, having a pH of 6.0, was admixed potassium tripolyphosphate at a concentration of 1.0 gram per liter, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a concentration of 0.3 grams per liter, as 0.375 milliliters of an 80 grams per liter stock solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide. The phosphate complexed solution was treated as described in Example 7. The solution clarity of the whey protein solution at pH 6.0 and pH 3.0, as indicated by percent trans-mittance at 625 millimicrons, were 8.3 and 18.0, respectively.
The solution clarities of the whey protein solutions were determined as previously described in Example 1 and are presented in Table II. It is clear from Examples 7 and 9 that improved solution clarity is obtained at both pH 6.0 and pH 3.0 by the optional addition of calcium chloride to the phosphate complexed solution.
To 100 milliliters of cheddar cheese whey obtained as described in Example 7, was admixed potassium tripolyphosphate at a concentration of 4.0 grams per liter, as 5 millimeters of an 80 grams per liter stock solution, to form a phosphate complexed solution. The remaining steps were as those described in Example 7.
The solution clarity of the whey protein solution at pH 6.0 and pH 3.0, as indicated by the percent transmittance at 625 millimicrons, were 64.5% and 66.2%, respectively. The solution clarities of the whey solutions were determined as previously described in E~xample 1 and are presented in Table II. It is clear from Examples 7, 8, and 9 of Table II that substantially improved results are obtained with the phosphate pretreating agent concentrations in the range of 4.0 grams per liter.
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; C-3512/3718 Examples 11-13 show the effect of phosphate removal on the protein concentration, phosphorus concentration, and the sol-ution clarity at pH 3.0 of the whey protein obtained in accor-dance with the present invention (Examples 11 and 13) compared to the control samples (Example 12).
To 700 milliliters of defatted cheese whey at a tem-perature of 125F. was admixed sodium acid pyrophosphate at a concentration of 4.0 grams per liter, as 35 milliliters of 80 grams per liter stock solution, to form a phosphate complexèd solution. The pH of the phosphate complexed solution was adjusted to 7.5 by the addition of sodium hydroxide to form a precipitate and a pretreated cheese whey solution. The precipitate was separated from the pretreated cheese whey solution by gravity lS filtration as previously described in ~xample 1 to give a separated precipitate and a separated pretreated cheese whey solution.
To the separated second cheese whey solution, heated to 125F., was admixed sodium polyphosphate (N ave. = 10.3) at a concentration of 9.0 grams per liter to form a protein-phosphate complexed solution. The pH of the protein-phosphate complexed solution was adjusted to 3.5 by the addition of hydrochloric acid to form a protein-phosphate precipitate and a supernatant solution.
The protein-phosphate precipitate was separated from the supernatant solution by filtration through number 541 Whatman Filter Paper. The separated protein-phosphate precipitate was dispersed in 100 milliliters of water by stirring the separated protein-phosphate precipitate in the water having a pH of 7.0 to form a protein-phosphate dispersion. 50 milliliters of the protein-phosphate dispersion was passed through an anionic ion exchange resin and freeze dried as described in Example 1.
The remaining 50 milliliters of the protein-phosphate dispersion was freeze dried without phosphate removal.
The protein concentrations of the treated whey protein product (phosphate removed) and the untreated whey protein product were determined in accordance with: Methods of Analysis, A.O.A.C., 16, tl970) 11th Ed., and are presented in Table III.
Also, the phosphorus concentration of the treated whey protein product and the untreated whey protein product were determined in accordance with Method of Analysis- A.O.A.C., 2.016, (1965) 10th Ed. and are presented in Table III.
The freeze dried treated whey protein and the untreated whey protein product were dissolved in water at a protein con-centration of 10 grams per liter. The pH of the whey protein solutions were adjusted to 3.0 as previously described in Example 1. The solution clarities of the whey protein solutions at pH 3.0, as indicated by percent light transmittance, at 625 millimicrons, were 38.8%, for the treated whey protein product and not calculable for the untreated whey protein product. The solution clarities were determined as previously described in Example 1, and are shown in Table III.
To 390 milliliters of defatted cheddar cheese whey obtained as described in Example 11, at a temperature of 125F., sodium polyphosphate (N ave. = 10.3) at a concentration of 9.0 grams per liter to form a protein-phosphate complexed solution.
The protein-phosphate complexed solution was thereafter treated as described in Example 11. The protein concentrations, and phosphate concentrations of the treated and untreated whey protein products were determined as described in Example 11, and are presented in Table III. The solution clarities of the whey protein solutions, i.e., treated and untreated, at pH 3.0, as indicated by the percent transmittance at 625 millimicrons were 1.3~, (treated), and not calculable (untreated) determined as previously described in Example 1, and are shown in Table III.
C-3~12/3718 It is clear from Examples 11 and 12 that pretreatment of cheese whey by the addition of the phosphate combined with phosphate removal provides whey protein products with increased protein concentration, reduced phosphate concentration, and substantially improved solution clarity at acid pH ~pH 3.0).
Example 13 shows the effect of pretreatment by the addition of the phosphate pretreating agent and the calcium chloride to provide improved results.
To 700 milliliters of defatted cheddar cheese whey at a temperature of 125F. was admixed sodium acid pyrophos-phate at a concentration of 4.0 grams per liter, as 35 milli-liters of an 80 grams per liter stock solution, to form a phosphate complexed solution. In addition, calcium chloride was admixed with the phosphate complexed solution at a con-centration of 1.14 grams per liter, as 10 milliliters of an 80 grams per liter stock solution. The pH of the phosphate complexed solution was ad]usted to 7.0 by the addition of sodium hydroxide. The phosphate complexed solution was thereafter treated as described in Example 11.
The separated protein-phosphate precipitate was d~is-persed in 250 milliliters of water by stirring the separated protein-phosphate precipitate in the water having a pH of about 7.0 to form a protein-phosphate dispersion. 125 milliliters of the protein-phosphate dispersion were passed through an anionic ion exchange resin and the effluent freeze dried, as previously described in Example 1.
The protein and phosphate concentrations of the treated and untreated whey protein products were determined as previously described in Example 11, and are presented in Table III. The freeze dried, treated and untreated, whey protein were products dissolved in water at a protein concentration of 10 grams per liter. The pH was adjusted to 3.0 as previously described in Example 1. The solution clarities of the whey protein solutions at pH 3.0, as indicated by the percent light transmittance at 625 millimicrons were 77.3~, (treated) and not calcuable (untreated) determined as previously described in Example 1, and are disclosed in Table III.
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Claims (15)
1. A process for the recovery of protein having improved solution clarity at acid pH from a proteinaceous aqueous solution containing whey protein comprising:
(a) admixing with a proteinaceous aqueous solution containing whey protein a phosphate selected from the group consisting of tetrasodium pyrophosphate, tetrapotassium pyro-phosphate, sodium acid pyrophosphate, potassium acid pyrophosphate, potassium tripolyphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, ammonium pyrophosphate, sodium iron pyrophosphate, or mixtures thereof at a concentration greater than 1.0 gram per liter to form a phosphate complexed solution;
(b) adjusting the pH of said phosphate complexed solution to a neutral range of from about 6.0 to about 8.0 by the addition of a base to form a precipitate and a pretreated proteinaceous aqueous solution containing whey protein;
(c) separating said precipitate from said pretreated proteinaceous aqueous solution to give a separated precipitated and a separated pretreated proteinaceous aqueous solution containing whey protein;
(d) admixing said separated pretreated proteinaceous aqueous solution with a medium chain length polyphosphate of the formula .
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000 to form a protein-phosphate complexed solution;
(e) adjusting the pH of said protein-phosphate complexed solution containing whey protein to an acid range of from about 4.5 to about 2.0 to form a protein-phosphate precipitate and a mineral solution;
(f) separating said protein-phosphate precipitate from said mineral solution;
(g) dispersing said separated protein-phosphate precipitate in an aqueous solution having a final pH from about 5.0 to about 12.0 to form a protein-phosphate dispersion;
(h) contacting said protein-phosphate dispersion with an anionic ion exchange resin to remove ionic phosphate from said dispersion and provide a proteinaceous effluent; and (i) recovering said proteinaceous effluent from said anionic ion exchange resin.
(a) admixing with a proteinaceous aqueous solution containing whey protein a phosphate selected from the group consisting of tetrasodium pyrophosphate, tetrapotassium pyro-phosphate, sodium acid pyrophosphate, potassium acid pyrophosphate, potassium tripolyphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tetrapolyphosphate, sodium tetrapolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, ammonium pyrophosphate, sodium iron pyrophosphate, or mixtures thereof at a concentration greater than 1.0 gram per liter to form a phosphate complexed solution;
(b) adjusting the pH of said phosphate complexed solution to a neutral range of from about 6.0 to about 8.0 by the addition of a base to form a precipitate and a pretreated proteinaceous aqueous solution containing whey protein;
(c) separating said precipitate from said pretreated proteinaceous aqueous solution to give a separated precipitated and a separated pretreated proteinaceous aqueous solution containing whey protein;
(d) admixing said separated pretreated proteinaceous aqueous solution with a medium chain length polyphosphate of the formula .
wherein X is selected from the group consisting of hydrogen and alkali metal; and Y is alkali metal; and N ave. represents an average chain length from about 3 to about 20,000 to form a protein-phosphate complexed solution;
(e) adjusting the pH of said protein-phosphate complexed solution containing whey protein to an acid range of from about 4.5 to about 2.0 to form a protein-phosphate precipitate and a mineral solution;
(f) separating said protein-phosphate precipitate from said mineral solution;
(g) dispersing said separated protein-phosphate precipitate in an aqueous solution having a final pH from about 5.0 to about 12.0 to form a protein-phosphate dispersion;
(h) contacting said protein-phosphate dispersion with an anionic ion exchange resin to remove ionic phosphate from said dispersion and provide a proteinaceous effluent; and (i) recovering said proteinaceous effluent from said anionic ion exchange resin.
2. The process of claim 1 wherein the average chain length of the polyphosphate is from about 8 to about 14 and at a concentration greater than 2.0 grams per liter.
3. The process of claim 1 wherein the pH of the phosphate complex is adjusted to about 6.5 to about 8Ø
4. The process of claim 1 wherein the aqueous solution to form the protein-phosphate dispersion has a final pH of from about 5.0 to about 8Ø
5. The process of claim 1 wherein said proteinaceous aqueous solution is cheese whey.
6. The process of claim 5 wherein said cheese whey is reconstituted dried cheese whey.
7. The process of claim 5 wherein said cheese whey is sweet cheese whey.
8. The process of claim 7 wherein said sweet cheese whey is selected from the group consisting of cheddar cheese whey, Swiss cheese whey, mozzarella cheese whey, or mixtures thereof.
9. The process of claim 1 which further includes admixing calcium chloride with said protein containing aqueous solution at a concentration from about 0.2 grams per liter to about 4.0 grams per liter.
10. The process of claim 9 wherein said proteinaceous aqueous solution is cheddar cheese whey, said phosphate is tetrasodium pyrophosphate, and said medium chain length poly-phosphate is sodium hexametaphosphate.
11. The process of claim 9 wherein said proteinaceous aqueous solution is cheddar cheese whey, said phosphate is sodium acid pyrophosphate, and said medium chain length poly-phosphate is sodium hexametaphosphate.
12. The process of claim 9 wherein said proteinaceous aqueous solution is cheddar cheese whey, said phosphate is potassium tripolyphosphate, and said medium chain length polyphosphate is sodium hexametaphosphate.
13. The process of claim 1 wherein said proteinaceous aqueous solution is cheddar cheese whey, said phosphate is sodium acid pyrophosphate, and said medium chain length poly-phosphate is sodium hexametaphosphate.
14. The process of claim 1 wherein said proteinaceous aqueous solution is cheddar cheese whey, said phosphate is potassium tripolyphosphate, and said medium chain length poly-phosphate is sodium hexametaphosphate.
15. Proteinaceous material whenever prepared or pro-duced by the process of claim 1 or by their obvious chemical equivalents.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US45289474A | 1974-03-20 | 1974-03-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1055931A true CA1055931A (en) | 1979-06-05 |
Family
ID=23798389
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA220,257A Expired CA1055931A (en) | 1974-03-20 | 1975-02-17 | Process for the recovery of protein having improved solution clarity |
Country Status (15)
Country | Link |
---|---|
AR (1) | AR211383Q (en) |
BE (1) | BE826945A (en) |
CA (1) | CA1055931A (en) |
CH (1) | CH611777A5 (en) |
DE (1) | DE2509516A1 (en) |
DK (1) | DK118875A (en) |
FI (1) | FI58430C (en) |
FR (1) | FR2264818B1 (en) |
GB (1) | GB1493677A (en) |
IE (1) | IE40669B1 (en) |
IT (1) | IT1032348B (en) |
NL (1) | NL7502751A (en) |
NO (1) | NO139766C (en) |
SE (1) | SE419693B (en) |
ZA (1) | ZA751000B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2671351A1 (en) * | 1991-01-03 | 1992-07-10 | Eurial | PROCESS FOR SEPARATING WHEY PROTEINS AND PRODUCTS OBTAINED |
-
1975
- 1975-02-17 CA CA220,257A patent/CA1055931A/en not_active Expired
- 1975-02-18 ZA ZA00751000A patent/ZA751000B/en unknown
- 1975-02-19 IE IE336/75A patent/IE40669B1/en unknown
- 1975-02-20 GB GB7149/75A patent/GB1493677A/en not_active Expired
- 1975-03-05 DE DE19752509516 patent/DE2509516A1/en not_active Withdrawn
- 1975-03-07 FI FI750666A patent/FI58430C/en not_active IP Right Cessation
- 1975-03-07 NL NL7502751A patent/NL7502751A/en not_active Application Discontinuation
- 1975-03-18 IT IT48658/75A patent/IT1032348B/en active
- 1975-03-19 SE SE7503159A patent/SE419693B/en unknown
- 1975-03-19 NO NO750942A patent/NO139766C/en unknown
- 1975-03-19 AR AR258029A patent/AR211383Q/en unknown
- 1975-03-19 CH CH351175A patent/CH611777A5/en not_active IP Right Cessation
- 1975-03-19 FR FR7508557A patent/FR2264818B1/fr not_active Expired
- 1975-03-20 DK DK118875A patent/DK118875A/da not_active Application Discontinuation
- 1975-03-20 BE BE7000631A patent/BE826945A/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
IE40669B1 (en) | 1979-07-18 |
FI58430B (en) | 1980-10-31 |
NL7502751A (en) | 1975-09-23 |
IT1032348B (en) | 1979-05-30 |
NO139766C (en) | 1979-05-09 |
NO750942L (en) | 1975-09-23 |
GB1493677A (en) | 1977-11-30 |
AR211383Q (en) | 1977-12-15 |
IE40669L (en) | 1975-09-20 |
AU7841175A (en) | 1976-08-26 |
FI58430C (en) | 1981-02-10 |
SE7503159L (en) | 1975-09-22 |
FI750666A (en) | 1975-09-21 |
DK118875A (en) | 1975-09-21 |
FR2264818B1 (en) | 1982-03-05 |
CH611777A5 (en) | 1979-06-29 |
ZA751000B (en) | 1976-01-28 |
DE2509516A1 (en) | 1975-09-25 |
NO139766B (en) | 1979-01-29 |
FR2264818A1 (en) | 1975-10-17 |
SE419693B (en) | 1981-08-24 |
BE826945A (en) | 1975-09-22 |
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