NO317162B1 - Stable preservative - Google Patents
Stable preservative Download PDFInfo
- Publication number
- NO317162B1 NO317162B1 NO20025472A NO20025472A NO317162B1 NO 317162 B1 NO317162 B1 NO 317162B1 NO 20025472 A NO20025472 A NO 20025472A NO 20025472 A NO20025472 A NO 20025472A NO 317162 B1 NO317162 B1 NO 317162B1
- Authority
- NO
- Norway
- Prior art keywords
- solution
- ascorbic acid
- kdf
- fish
- propyl gallate
- Prior art date
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- 239000003755 preservative agent Substances 0.000 title claims description 29
- 230000002335 preservative effect Effects 0.000 title claims description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 118
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical group CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 104
- 239000000243 solution Substances 0.000 claims description 80
- 235000010323 ascorbic acid Nutrition 0.000 claims description 59
- 239000011668 ascorbic acid Substances 0.000 claims description 59
- 229960005070 ascorbic acid Drugs 0.000 claims description 59
- 235000010388 propyl gallate Nutrition 0.000 claims description 52
- 239000000473 propyl gallate Substances 0.000 claims description 52
- 229940075579 propyl gallate Drugs 0.000 claims description 52
- 239000003963 antioxidant agent Substances 0.000 claims description 30
- 235000006708 antioxidants Nutrition 0.000 claims description 30
- 230000007797 corrosion Effects 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 45
- 241000251468 Actinopterygii Species 0.000 description 38
- 235000019688 fish Nutrition 0.000 description 38
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 32
- 238000003860 storage Methods 0.000 description 32
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 16
- 235000019253 formic acid Nutrition 0.000 description 16
- 235000014655 lactic acid Nutrition 0.000 description 14
- 239000004310 lactic acid Substances 0.000 description 14
- 235000011054 acetic acid Nutrition 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 235000013332 fish product Nutrition 0.000 description 9
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- 235000011085 potassium lactate Nutrition 0.000 description 6
- 239000001521 potassium lactate Substances 0.000 description 6
- 229960001304 potassium lactate Drugs 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 241001417902 Mallotus villosus Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- BINNZIDCJWQYOH-UHFFFAOYSA-M potassium;formic acid;formate Chemical compound [K+].OC=O.[O-]C=O BINNZIDCJWQYOH-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000252203 Clupea harengus Species 0.000 description 2
- 235000019733 Fish meal Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004467 fishmeal Substances 0.000 description 2
- 235000019514 herring Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000011732 tocopherol Substances 0.000 description 2
- 229930003799 tocopherol Natural products 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- NPCOQXAVBJJZBQ-UHFFFAOYSA-N reduced coenzyme Q9 Natural products COC1=C(O)C(C)=C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)C(O)=C1OC NPCOQXAVBJJZBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- -1 salts potassium lactate Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229940040064 ubiquinol Drugs 0.000 description 1
- QNTNKSLOFHEFPK-UPTCCGCDSA-N ubiquinol-10 Chemical compound COC1=C(O)C(C)=C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(O)=C1OC QNTNKSLOFHEFPK-UPTCCGCDSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
- A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
- A23B4/20—Organic compounds; Microorganisms; Enzymes
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
- A23L3/3517—Carboxylic acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Meat, Egg Or Seafood Products (AREA)
Description
Stabilt konserveringsmiddel. Stable preservative.
Foreliggende oppfinnelse vedrører et konserveringsmiddel. The present invention relates to a preservative.
Det er ofte påkrevd å lagre fisk, fiskeprodukter og fiskebiprodukter for en lengre periode. Et hovedproblem i denne forbindelse har vært å oppnå en effektiv konservering av nevnte produkter og å oppnå et konservert fiskemateriale av påkrevd kvalitet for videre foredling, både med hensyn til konsistens og degradering på grunn av enzymatisk og bakteriell aktivitet. It is often required to store fish, fish products and fish by-products for a longer period. A main problem in this regard has been to achieve an effective conservation of said products and to achieve a preserved fish material of the required quality for further processing, both with regard to consistency and degradation due to enzymatic and bacterial activity.
Anvendelse av konserveringsmidler er generelt kjent. Løsninger av karboksylsyrer og deres salter, spesielt eddiksyre eller maursyre og kaliumdiformiat (KDF) er kjent som konserveringsmidler for fisk, fiskeprodukter og fiskebiprodukter. Nedbrytningsproses-sene av fiskeråmaterialet hemmes og således blir kvaliteten til råmaterialet forbedret. Dette resulterer i en forlenget lagringsperiode for fiskeproduktene før videre foredling, som for eksempel fiskemelproduksjon. Uansett så ville det være av interesse å ytterligere hemme oksidasjon av oljen under lagring av fiskeproduktene og det ville også være ønskelig å redusere utviklingen av totalt flyktig basisk nitrogen (TVB-N). Tilsetning av en antioksidant kan løse problemene med oksidasjon og TVB-N utvikling, men da er problemet å finne en antioksidant som ikke vil felle ut fra den konserverende løsningen over tid. Det kunne også være av interesse å redusere korrosjon forårsaket av den konserverende løsning ved å tilsette en korrosjonsinhibitor. The use of preservatives is generally known. Solutions of carboxylic acids and their salts, especially acetic or formic acid and potassium diformate (KDF) are known as preservatives for fish, fish products and fish by-products. The degradation processes of the fish raw material are inhibited and thus the quality of the raw material is improved. This results in an extended storage period for the fish products before further processing, such as fish meal production. In any case, it would be of interest to further inhibit oxidation of the oil during storage of the fish products and it would also be desirable to reduce the development of total volatile basic nitrogen (TVB-N). Adding an antioxidant can solve the problems with oxidation and TVB-N development, but then the problem is to find an antioxidant that will not precipitate from the preservative solution over time. It could also be of interest to reduce corrosion caused by the preservative solution by adding a corrosion inhibitor.
US 5,993,875 vedrører en fremgangsmåte for kjøling og konservering av fisk og produkter fremstilt fra slik behandlet fisk. Fisken kjøles ved hjelp av et kjølemedium i tan-ker, beholdere eller andre egnede lagringsutstyr, og utsettes også for en behandling av i det minste ett konserveringsmiddel. Fisken utsettes for en kombinert behandling av et kjølemedium og et konserverende middel og nevnte behandling utføres ved hjelp av et kjølemedium omfattende Ci^ monokarboksylsyrer og/eller mono-/di- eller tetrasalter av alkali- og/eller jordalkal i salter av nevnte syrer. Kjølingen utføres ved hjelp av et kjøle-medium, som er en vandig løsning av Cw monokarboksyliske salter i en konsentrasjon på 5-30 vekt % salter og 97-70 vekt % vann, eller binær is omfattende et konserveringsmiddel. Den mest foretrukne lake eller binære is omfatter kaliumformiat og/eller kaliumdiformiat og/eller maursyre. Lakens pH kan justeres ved tilsats av en syre eller disalt som er ekvivalent til monosaltet anvendt i laken. US 5,993,875 relates to a method for cooling and preserving fish and products made from such treated fish. The fish is cooled using a cooling medium in tanks, containers or other suitable storage equipment, and is also subjected to a treatment of at least one preservative. The fish is subjected to a combined treatment of a cooling medium and a preservative and said treatment is carried out with the help of a cooling medium comprising Ci^ monocarboxylic acids and/or mono-/di- or tetrasalts of alkali and/or alkaline earth in salts of said acids. The cooling is carried out using a cooling medium, which is an aqueous solution of Cw monocarboxylic salts in a concentration of 5-30% by weight of salts and 97-70% by weight of water, or binary ice comprising a preservative. The most preferred brine or binary ice comprises potassium formate and/or potassium diformate and/or formic acid. The bed's pH can be adjusted by adding an acid or disalt that is equivalent to the monosalt used in the bed.
Fiskeproduktene må utsettes for en kombinert behandling av et kjølemedium og et konserveringsmiddel. Det ville være av interesse å tilveiebringe et konserveirngsmiddel som ville gi en forlenget lagringsperiode uten et kjølemedium. The fish products must be subjected to a combined treatment of a cooling medium and a preservative. It would be of interest to provide a preservative that would provide an extended storage period without a refrigerant.
WO 01/32040 Al vedrører en fremgangsmåte for å redusere oksidasjon i matvarer ved selektivt å tilsette en eller flere antioksidanter til den polare lipidfraksjonen av et matva-reprodukt. Et organisk løsningsmiddel som er blandbart med vann anvendes for å løse antioksidantene. Antioksidantene kan være tokoferol, karotenoid, ubikinol, butylert hydroksyanisol, butylert hydroksytoluen, propylgallat eller r-butylhydrokinon. Det er ikke ønskelig å anvende et organisk løsningsmiddel i et konserveringsmiddel for fiskeprodukter og de fleste av antioksidantene ville ikke være løselige i den konserverende løsningen. Selv om det skulle være mulig å løse noen antioksidanter uten løsningsmid-del ville de felle ut under lagring. WO 01/32040 Al relates to a method for reducing oxidation in foodstuffs by selectively adding one or more antioxidants to the polar lipid fraction of a food product. An organic solvent that is miscible with water is used to dissolve the antioxidants. The antioxidants can be tocopherol, carotenoid, ubiquinol, butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate or r-butylhydroquinone. It is not desirable to use an organic solvent in a preservative for fish products and most of the antioxidants would not be soluble in the preservative solution. Even if it were possible to dissolve some antioxidants without a solvent component, they would precipitate during storage.
NO-B1-309796 vedrører et ensileringsmiddel som omfatter en oppløsning av minst en antioksidant og en kortkjedet karboksylsyre, og eventuelt et salt av den nevnte syre. Det nevnes at ensileringsmiddelet også kan omfatte andre tilsetningsstoffer, men det er ikke nevnt noe om tilsetningsstoffer for å stabilisere antioksidanter. NO-B1-309796 relates to an ensiling agent which comprises a solution of at least one antioxidant and a short-chain carboxylic acid, and optionally a salt of the aforementioned acid. It is mentioned that the ensiling agent may also include other additives, but nothing is mentioned about additives to stabilize antioxidants.
Hovedformålet til foreliggende oppfinnelse var å komme frem til et konserveringsmiddel som ikke ville gi utfelling av antioksidanten under lagring. The main purpose of the present invention was to arrive at a preservative which would not precipitate the antioxidant during storage.
Et annet formål var å redusere korrosjon av konserveringsmiddelet. Another purpose was to reduce corrosion of the preservative.
Et ytterligere formål var å oppnå et konserveirngsmiddel som ville gi en forlenget lagringsperiode for fisk, fiskeprodukter og fiskebiprodukter, særlig med hensyn på dets li-pidinnhold, før fiskemelproduksjon. A further aim was to achieve a preservative which would provide an extended storage period for fish, fish products and fish by-products, particularly with regard to its lipid content, before fishmeal production.
Disse og andre formål med oppfinnelsen ble oppnådd ved produktet som beskrevet ne-denfor. Oppfinnelsen er ytterligere karakterisert ved patentkravene. These and other objects of the invention were achieved by the product as described below. The invention is further characterized by the patent claims.
For å løse formålet med oppfinnelsen forsøkte oppfinnerne å tilsette en antioksidant til en vandig løsning omfattende 20 - 80 vekt % av Ci - C3 karboksylsyrer i blanding med deres salter. Det ble funnet at en foretrukket vandig sammensetning ville være maursyre og/eller eddiksyre og/eller melkesyre i kombinasjon med deres salter, og at kationet kunne være natrium og/eller kalium og/eller kalsium og/eller magnesium. Mest foretrukket skulle kationet være kalium. Minst 50 mol % av karboksylsyrene skulle være i udissosiert form. In order to solve the object of the invention, the inventors attempted to add an antioxidant to an aqueous solution comprising 20-80% by weight of Ci-C3 carboxylic acids in mixture with their salts. It was found that a preferred aqueous composition would be formic acid and/or acetic acid and/or lactic acid in combination with their salts, and that the cation could be sodium and/or potassium and/or calcium and/or magnesium. Most preferably, the cation should be potassium. At least 50 mol% of the carboxylic acids should be in undissociated form.
Det ble funnet at de fleste av de godkjente antioksidanter ikke var særlig løselige i løs-ninger av karboksylsyrer og deres salter. Dette gjelder for eksempel butylert hydroksytoluen (BHT), butylert hydroksyanisol (BHA), tokoferoler og etoksykin. Andre antioksidanter, slik som askorbinsyre, hadde ingen antioksidativ effekt. Av de undersøkte antioksidanter var det bare gal låtene som var løselige, men de gav utfelling over tid. Siden et av formålene var å redusere korrosjon av konserveringsmiddelet, var det ønskelig å finne en korrosjonsinhibitor som ville være kompatibel med antioksidanten. Det ble da overrasket funnet at når askorbinsyre (AS) ble tilsatt som en korrosjonsinhibitor, viste forsøk at propylgallat (PG) ikke felte ut. Korrosjonsinhibitoren hadde således to positive effekter. Korrosjonsinhibitoren stabiliserte antioksidanten slik at antioksidanten ikke ble utfelt over tid, og korrosjon forårsaket av konserveringsmiddelet ble betydelig redusert. Den foreliggende oppfinnelse vil i sitt videste omfang omfatte et stabilt konserveringsmiddel omfattende en vandig løsning av Ci - C3 karboksylsyrer i blanding med deres salter, hvor nevnte løsning omfatter 20 - 80 vekt % Ci - C3 karboksylsyrer i blanding med deres salter, 0,01-2 vekt % antioksidant som er et gallat og 0,01-2 vekt % korrosjonsinhibitor som er askorbinsyre. Innholdet av gallat er foretrukket 0,25 - 1,5 vekt % og innholdet av askorbinsyre er foretrukket 0,25 - 1,5 vekt %. Gallatet er foretrukket propylgallat. Karboksylsyrene er maursyre og/eller eddiksyre og/eller melkesyre. Kationet er foretrukket kalium. Minst 50 mol % av karboksylsyrene er i udissosiert form. It was found that most of the approved antioxidants were not very soluble in solutions of carboxylic acids and their salts. This applies, for example, to butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tocopherols and ethoxyquin. Other antioxidants, such as ascorbic acid, had no antioxidant effect. Of the investigated antioxidants, only gal songs were soluble, but they precipitated over time. Since one of the purposes was to reduce corrosion of the preservative, it was desirable to find a corrosion inhibitor that would be compatible with the antioxidant. It was then surprisingly found that when ascorbic acid (AS) was added as a corrosion inhibitor, experiments showed that propyl gallate (PG) did not precipitate. The corrosion inhibitor thus had two positive effects. The corrosion inhibitor stabilized the antioxidant so that the antioxidant was not precipitated over time, and corrosion caused by the preservative was significantly reduced. In its broadest scope, the present invention will encompass a stable preservative comprising an aqueous solution of Ci - C3 carboxylic acids in a mixture with their salts, where said solution comprises 20 - 80% by weight Ci - C3 carboxylic acids in a mixture with their salts, 0.01- 2% by weight antioxidant which is a gallate and 0.01-2% by weight corrosion inhibitor which is ascorbic acid. The content of gallate is preferably 0.25 - 1.5% by weight and the content of ascorbic acid is preferably 0.25 - 1.5% by weight. The gallate is preferably propyl gallate. The carboxylic acids are formic and/or acetic and/or lactic acid. The cation is preferably potassium. At least 50 mol% of the carboxylic acids are in undissociated form.
Oppfinnelsen er nærmere beskrevet og forklart i de følgende eksempler og figurer. Figur 1 viser utfelling i vandig løsninger av maursyre, eddiksyre og melkesyre i blandinger med kaliumformiat med propylgallat og med og uten tilsats av askorbinsyre. Figur 2 viser utfelling i vandige løsninger av eddiksyre og melkesyre i blandinger med maursyre, kaliumacetat eller kaliumlaktat med propylgallat og med og uten tilsats av askorbinsyre. Figur 3 viser korrosjon for en kaliumdiforrniat (KDF) løsning med ulike konsentrasjoner av askorbinsyre. Figur 4 viser korrosjon for en kaliumdiforrniat (KDF) løsning omfattende propylgallat og askorbinsyre sammenlignet med en KDF løsning. Figur 5 viser TVB-N utvikling i fisk behandlet med forskjellige KDF løsninger. Figur 6 viser TVB-N utvikling i biprodukter behandlet med forskjellige KDF The invention is further described and explained in the following examples and figures. Figure 1 shows precipitation in aqueous solutions of formic acid, acetic acid and lactic acid in mixtures with potassium formate with propyl gallate and with and without the addition of ascorbic acid. Figure 2 shows precipitation in aqueous solutions of acetic acid and lactic acid in mixtures with formic acid, potassium acetate or potassium lactate with propyl gallate and with and without the addition of ascorbic acid. Figure 3 shows corrosion for a potassium diforrniate (KDF) solution with different concentrations of ascorbic acid. Figure 4 shows corrosion for a potassium diforrniate (KDF) solution comprising propyl gallate and ascorbic acid compared to a KDF solution. Figure 5 shows TVB-N development in fish treated with different KDF solutions. Figure 6 shows TVB-N development in by-products treated with different KDF
løsninger. solutions.
Figur 7 viser TVB-N utvikling i lodde ved forskjellige temperaturer. Figure 7 shows TVB-N development in solder at different temperatures.
Figur 8 viser TVB-N utvikling i lodde i KDF løsninger med forskjellige konsentrasjoner. Figure 8 shows TVB-N development in solder in KDF solutions with different concentrations.
Figur 9 viser effekt på oksidasjon av olje under lagring. Figure 9 shows the effect on oxidation of oil during storage.
Eksempel 1 Example 1
Eksempel 1 ble utført for å undersøke utfellingen av propylgallat i forskjellige løsninger av Ci - C3 karboksylsyrer i blanding med deres salter eksemplifisert med maursyre, eddiksyre og melkesyre, og saltet kaliumformiat. Example 1 was carried out to investigate the precipitation of propyl gallate in various solutions of Ci - C3 carboxylic acids in mixture with their salts exemplified by formic acid, acetic acid and lactic acid, and salted potassium formate.
Løsninger ble tillaget med maursyre, eddiksyre og melkesyre i kombinasjon med kaliumformiat. Hver av løsningene ble laget i duplikat og tilsatt 1 vekt % propylgallat. En av parallellene ble tilsatt 1,25 vekt % askorbinsyre. Askorbinsyre ble tilsatt på bekostning av vann. De forskjellige formuleringene er vist i Tabell 1. Solutions were prepared with formic acid, acetic acid and lactic acid in combination with potassium formate. Each of the solutions was made in duplicate and 1% by weight propyl gallate was added. One of the parallels was added with 1.25% by weight ascorbic acid. Ascorbic acid was added at the expense of water. The different formulations are shown in Table 1.
Tabell 1 viser formuleringer av propylgallat i løsninger av maursyre, eddiksyre og melkesyre i blandinger med kaliumformiat. Hver formulering ble tillaget med og uten askorbinsyre. Table 1 shows formulations of propyl gallate in solutions of formic acid, acetic acid and lactic acid in mixtures with potassium formate. Each formulation was prepared with and without ascorbic acid.
Løsningen ble oppbevart i romtemperatur i en periode på 6 måneder. Etter lagringsperioden på 6 måneder ble prøvene filtrert ved å anvende et membranfilter (SS 3.0um). The solution was stored at room temperature for a period of 6 months. After the storage period of 6 months, the samples were filtered using a membrane filter (SS 3.0um).
Fig. 1 viser utfelling i vandige løsninger av maursyre, eddiksyre og melkesyre i blandinger med kaliumdiforrniat med propylgallat og med og uten tilsats av askorbinsyre. Fig. 1 shows precipitation in aqueous solutions of formic acid, acetic acid and lactic acid in mixtures with potassium diforrniate with propyl gallate and with and without the addition of ascorbic acid.
Som kan sees fra Fig. 1, ble bare ubetydelig bunnfall funnet i løsningene hvor propylgallat var tilsatt i kombinasjon med askorbinsyre, mens betydelige mengder utfelling ble funnet i løsningene uten askorbinsyre. As can be seen from Fig. 1, only negligible precipitation was found in the solutions where propyl gallate was added in combination with ascorbic acid, while significant amounts of precipitation were found in the solutions without ascorbic acid.
Tilsats av askorbinsyre (1,25 vekt %) ble funnet å stabilisere propylgallat (1 vekt %) i vandige løsninger omfattende maursyre, eddiksyre og melkesyre i kombinasjon med kaliumformiat. Addition of ascorbic acid (1.25 wt %) was found to stabilize propyl gallate (1 wt %) in aqueous solutions comprising formic acid, acetic acid and lactic acid in combination with potassium formate.
Eksempel 2 Example 2
Eksempel 2 ble utført for å undersøke utfellingen av propylgallat i forskjellige løsninger av Ci - C3 karboksylsyrer i blanding med deres salter eksemplifisert med maursyre, eddiksyre og melkesyre, og saltene kaliumlaktat og kaliumacetat. Example 2 was carried out to investigate the precipitation of propyl gallate in various solutions of Ci - C3 carboxylic acids in mixture with their salts exemplified by formic acid, acetic acid and lactic acid, and the salts potassium lactate and potassium acetate.
Vandige løsninger ble tillaget med eddiksyre eller melkesyre alene eller i kombinasjon med maursyre, kaliumacetat eller kaliumlaktat. Hver av løsningene ble laget i duplikat og alle løsningene ble tilsatt 1 vekt % propylgallat. En av parallellene ble tilsatt 1,25 vekt % askorbinsyre. Askorbinsyre ble tilsatt på bekostning av vann. De forskjellige formuleringene er vist i Tabell 2. Aqueous solutions were prepared with acetic acid or lactic acid alone or in combination with formic acid, potassium acetate or potassium lactate. Each of the solutions was made in duplicate and all solutions were supplemented with 1% by weight propyl gallate. One of the parallels was added with 1.25% by weight ascorbic acid. Ascorbic acid was added at the expense of water. The different formulations are shown in Table 2.
Tabell 2 viser formuleringer av propylgallat i løsninger av eddiksyre og melkesyre alene eller i kombinasjon med maursyre og/eller kaliumlaktat eller kaliumacetat. Hver formulering ble tillaget med og uten askorbinsyre. Table 2 shows formulations of propyl gallate in solutions of acetic acid and lactic acid alone or in combination with formic acid and/or potassium lactate or potassium acetate. Each formulation was prepared with and without ascorbic acid.
Løsningen ble oppbevart i romtemperatur i en periode på 2 måneder. Etter lagringsperioden på 2 måneder ble prøvene filtrert ved å anvende et membranfilter (SS 3.0um). The solution was stored at room temperature for a period of 2 months. After the storage period of 2 months, the samples were filtered using a membrane filter (SS 3.0um).
Fig. 2 viser utfelling i vandige løsninger av eddiksyre og melkesyre i blandinger med maursyre, kaliumacetat eller kaliumlaktat med propylgallat og med og uten tilsats av askorbinsyre. Fig. 2 shows precipitation in aqueous solutions of acetic acid and lactic acid in mixtures with formic acid, potassium acetate or potassium lactate with propyl gallate and with and without the addition of ascorbic acid.
Som kan sees fra Fig. 2, ble bare ubetydelig eller ikke påviselig bunnfall funnet i løs-ningene hvor propylgallat var tilsatt i kombinasjon med askorbinsyre, mens betydelige mengder utfelling ble funnet i løsningene uten askorbinsyre. As can be seen from Fig. 2, only insignificant or undetectable precipitation was found in the solutions where propyl gallate was added in combination with ascorbic acid, while significant amounts of precipitation were found in the solutions without ascorbic acid.
Tilsats av askorbinsyre (1,25 vekt %) ble funnet å stabilisere propylgallat (1 vekt %) i vandige løsninger av eddiksyre eller melkesyre alene eller i kombinasjon med maursyre og/eller kaliumacetat eller kaliumlaktat. Addition of ascorbic acid (1.25 wt %) was found to stabilize propyl gallate (1 wt %) in aqueous solutions of acetic acid or lactic acid alone or in combination with formic acid and/or potassium acetate or potassium lactate.
Eksempel 3 Example 3
Et forsøk ble utført for å sjekke utfelling av propylgallat (PG) i kaliumdiforrniat (KDF) løsninger med og uten tilsats av askorbinsyre (AS) An experiment was carried out to check the precipitation of propyl gallate (PG) in potassium diforrniate (KDF) solutions with and without the addition of ascorbic acid (AS)
En KDF løsning (30 vekt % kaliumdiformiatløsning i vann) med 0,5 vekt % propylgallat og en KDF løsning (30 vekt % løsning i vann) med 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre ble undersøkt. Resultatene er vist i Tabell 3. A KDF solution (30 wt% potassium diformate solution in water) with 0.5 wt% propyl gallate and a KDF solution (30 wt% solution in water) with 0.5 wt% propyl gallate and 0.5 wt% ascorbic acid were investigated. The results are shown in Table 3.
Som kan sees fra Tabell 3 er det ingen utfelling i KDF løsningen omfattende propylgallat og askorbinsyre, mens det er utfelling i alle løsningene uten askorbinsyre. Tilsats av 0,5 vekt % askorbinsyre stabiliserer en konsentrasjon av 0,5 vekt % propylgallat i vandige løsninger omfattende blandinger av kaliumformiat og maursyre (30 vekt %). As can be seen from Table 3, there is no precipitation in the KDF solution comprising propyl gallate and ascorbic acid, while there is precipitation in all the solutions without ascorbic acid. Addition of 0.5% by weight ascorbic acid stabilizes a concentration of 0.5% by weight propyl gallate in aqueous solutions comprising mixtures of potassium formate and formic acid (30% by weight).
Eksempel 4 Example 4
Et dose-respons eksperiment ble utført for å bestemme forholdet mellom dosering av askorbinsyre og korrosjonshemming i en KDF løsning. A dose-response experiment was carried out to determine the relationship between dosage of ascorbic acid and corrosion inhibition in a KDF solution.
Tre plater ulegert stål (40 x 30 x 2 mm) ble nedsenket i løsninger inneholdende 1,4 vekt % KDF (30 vekt % løsning i vann) med forskjellige konsentrasjoner av askorbinsyre og en kontrolløsning av 1,4 vekt % KDF (30 vekt % løsning i vann). Forsøket ble utført ved romtemperatur i 7 dager. pH under forsøksperioden var 3,7. Prøvene ble anbrakt på glasstativ med glasskroker og plassert i begre inneholdende prøveløsningene. Magnetiske rørere ble anvendt for å sirkulere løsningene. Etter utsetting ble prøvene ultrasonisk renset i inhibert saltsyre, såpevann, springvann og aceton. Korrosjonshastighetene ble beregnet fra vekttap. Three plates of unalloyed steel (40 x 30 x 2 mm) were immersed in solutions containing 1.4 wt % KDF (30 wt % solution in water) with different concentrations of ascorbic acid and a control solution of 1.4 wt % KDF (30 wt % solution in water). The experiment was carried out at room temperature for 7 days. The pH during the experimental period was 3.7. The samples were placed on glass stands with glass hooks and placed in beakers containing the sample solutions. Magnetic stirrers were used to circulate the solutions. After exposure, the samples were ultrasonically cleaned in inhibited hydrochloric acid, soapy water, tap water and acetone. The corrosion rates were calculated from weight loss.
Resultatet av forsøket er vist i Fig. 3. Konsentrasjonen av askorbinsyre er gitt som pro-sentdel askorbinsyre i lagringsløsningen (30 vekt % KDF i vann). Som kan sees fra Figuren, reduserer tilsats av askorbinsyre (0,5 vekt % eller høyere til lagringsløsningen) korrosjonshastigheten med 40 - 42 %. The result of the experiment is shown in Fig. 3. The concentration of ascorbic acid is given as a percentage of ascorbic acid in the storage solution (30% by weight KDF in water). As can be seen from the Figure, the addition of ascorbic acid (0.5% by weight or higher to the storage solution) reduces the corrosion rate by 40 - 42%.
Eksempel 5 Example 5
Den korrosjonshemmende effekten til askorbinsyre ble undersøkt i en løsning av KDF og propylgallat. The corrosion-inhibiting effect of ascorbic acid was investigated in a solution of KDF and propyl gallate.
Tre plater ulegert stål (40 x 30 x 2 mm) ble nedsenket i løsninger inneholdende 1,4 vekt % KDF (30 vekt % løsning i vann) med 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre og en kontrolløsning av 1,4 vekt % KDF. Forsøket ble utført ved 3 og 22 °C i 7 dager ved en pH på 6,0. Prøvene ble anbrakt på glasstativ med glasskroker og plassert i begre inneholdende prøveløsningene. Magnetiske rørere ble anvendt for å sirkulere løs-ningene. Etter utsetting ble prøvene ultrasonisk renset i inhibert saltsyre, såpevann, springvann og aceton. Korrosjonshastighetene ble beregnet fra vekttap. Three plates of unalloyed steel (40 x 30 x 2 mm) were immersed in solutions containing 1.4 wt % KDF (30 wt % solution in water) with 0.5 wt % propyl gallate and 0.5 wt % ascorbic acid and a control solution of 1 .4 wt% KDF. The experiment was carried out at 3 and 22 °C for 7 days at a pH of 6.0. The samples were placed on glass stands with glass hooks and placed in beakers containing the sample solutions. Magnetic stirrers were used to circulate the solutions. After exposure, the samples were ultrasonically cleaned in inhibited hydrochloric acid, soapy water, tap water and acetone. The corrosion rates were calculated from weight loss.
Resultatet av forsøket er vist i Fig. 4. Som kan sees fra Figuren, ble reduserte korro-sjonshastigheter observert ved den lavere temperaturen både for kontrollen og løsningen med propylgallat og askorbinsyre. Ved 3 °C ble korrosjonshastigheten redusert med 54 % i løsningen inneholdende propylgallat og askorbinsyre og ved 22 °C ble korrosjonshastigheten redusert med 26 %. The result of the experiment is shown in Fig. 4. As can be seen from the Figure, reduced corrosion rates were observed at the lower temperature for both the control and the solution with propyl gallate and ascorbic acid. At 3 °C the corrosion rate was reduced by 54% in the solution containing propyl gallate and ascorbic acid and at 22 °C the corrosion rate was reduced by 26%.
Eksempel 6 Example 6
Et eksperiment i pilotskala ble utført for å undersøke effekten av å tilsette gallater til en KDF løsning på lagringsstabiliteten til fisk uttrykt som utviklingen av totalt flyktig nitrogen (TVB-N). A pilot-scale experiment was carried out to investigate the effect of adding gallates to a KDF solution on the storage stability of fish expressed as the development of total volatile nitrogen (TVB-N).
Totalt 6 beholdere (3 liter med lokk) ble hver tilsatt 2,5 kg lodde. Lodden hadde vært frosset før eksperimentet og var av god kvalitet (TVB-N - 7.7 mg/100 g fisk). Råmaterialet ble tilsatt 1,4 vekt % KDF(30 vekt % løsning i vann) med 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre eller 1,4 vekt % KDF (30 vekt % løsning i vann) uten antioksidant og korrosjonsinhibitor. Behandlingene ble tillaget med en parallell og sammenlignet med en kontroll uten tilsats av KDF. Temperatur og pH ble registrert under eksperimentet og TVB-N ble analysert. Resultatene fra TVB-N analysene ble utsatt for ikke-lineære regresjonsanalyser. A total of 6 containers (3 liters with lids) were each added with 2.5 kg of solder. The capelin had been frozen before the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish). The raw material was supplemented with 1.4 wt % KDF (30 wt % solution in water) with 0.5 wt % propyl gallate and 0.5 wt % ascorbic acid or 1.4 wt % KDF (30 wt % solution in water) without antioxidant and corrosion inhibitor . The treatments were prepared in parallel and compared with a control without the addition of KDF. Temperature and pH were recorded during the experiment and TVB-N was analyzed. The results from the TVB-N analyzes were subjected to non-linear regression analyses.
Gjennomsnittstemperaturen under lagringsperioden var 5,6 °C (0.2) og pH var i området fra 6,0 til 6,2 i behandlingene tilsatt 1,4 vekt % KDF (med eller uten antioksidant og korrosjonsinhibitor) og en pH fra 6,5 til 6,7 i kontrollen. Fig. 5 viser TVB-N utviklingen i lodde under lagring. Som kan sees fra Figuren, reduserte KDF løsningen omfattende propylgallat og askorbinsyre TVB-N utviklingen og forlenget således lagringsperioden for fisken. Etter 17 dagers lagring var TVB-N verdien så vidt over 40 mg/100 g fisk for fisk behandlet med KDF løsningen omfattende propylgallat og askorbinsyre, mens fisk behandlet med bare KDF løsning nådde denne TVB-N verdien etter omtrent 11 dager, og kontrollen uten tilsats nådde samme verdi etter omtrent 6,5 dagers lagring. Det ble funnet at propylgallat forlenget lagringsperioden med 6 dager sammenlignet med KDF løsningen uten antioksidant. The average temperature during the storage period was 5.6 °C (0.2) and the pH was in the range from 6.0 to 6.2 in the treatments added 1.4 wt% KDF (with or without antioxidant and corrosion inhibitor) and a pH from 6.5 to 6.7 in the control. Fig. 5 shows the TVB-N development in solder during storage. As can be seen from the Figure, the KDF solution comprising propyl gallate and ascorbic acid reduced TVB-N development and thus extended the storage period for the fish. After 17 days of storage, the TVB-N value was barely above 40 mg/100 g of fish for fish treated with the KDF solution including propyl gallate and ascorbic acid, while fish treated with only the KDF solution reached this TVB-N value after approximately 11 days, and the control without additive reached the same value after approximately 6.5 days of storage. It was found that propyl gallate extended the storage period by 6 days compared to the KDF solution without antioxidant.
Eksempel 7 Example 7
Dette eksperiment ble utført for å undersøke effekten av å tilsette antioksidanter på TVB-N utviklingen av biprodukter under lagring. This experiment was conducted to investigate the effect of adding antioxidants on TVB-N the development of by-products during storage.
Avskjær av sild ble tilsatt 1,5 vekt % KDF (30 vekt % løsning i vann) med eller uten tilsats av antioksidanter og askorbinsyre. Tilsatsen ble gjort som en vekt - til - vekt pro-sentandel. Avskjæret ble delt i 6 beholdere (1 liter), 600 g hver. To av beholderne ble beholdt som en kontroll uten KDF tilsetning, to beholdere ble tilsatt KDF (30 vekt % løsning i vann) og to av beholderne en blanding av KDF (30 vekt % løsning i vann) og 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre. Fisken ble lagret ved 5°C og TVB-N analysert. Herring trimmings were added with 1.5% by weight KDF (30% by weight solution in water) with or without the addition of antioxidants and ascorbic acid. The addition was made as a weight-to-weight percentage. The cuttings were divided into 6 containers (1 litre), 600 g each. Two of the containers were kept as a control without KDF addition, two containers were supplemented with KDF (30 wt% solution in water) and two of the containers a mixture of KDF (30 wt% solution in water) and 0.5 wt% propyl gallate and 0 .5% by weight ascorbic acid. The fish were stored at 5°C and TVB-N analyzed.
TVB-N utviklingen i de forskjellige behandlingene er vist i Fig. 6. Som kan sees fra Figuren, ble det funnet at tilsats av antioksidanter reduserte TVB-N utviklingen. I kontrollen økte TVB-N raskt og nådde en TVB-N verdi på 40 etter tilnærmet 3,5 dager. For bi-produktene omfattende KDF og KDF med propylgallat og askorbinsyre var TVB-N utviklingen lavere og lagringsperioden var henholdsvis 6 og 8 dager. Det ble funnet at tilsats av propylgallat økte lagringsperioden med 2 dager sammenlignet med KDF løsning uten antioksidant. The TVB-N development in the different treatments is shown in Fig. 6. As can be seen from the figure, it was found that the addition of antioxidants reduced the TVB-N development. In the control, TVB-N increased rapidly and reached a TVB-N value of 40 after approximately 3.5 days. For the by-products comprising KDF and KDF with propyl gallate and ascorbic acid, TVB-N development was lower and the storage period was 6 and 8 days respectively. It was found that the addition of propyl gallate increased the storage period by 2 days compared to KDF solution without antioxidant.
Eksempel 8 Example 8
Et eksperiment i pilotskala ble utført for å undersøke effekten av forskjellige temperaturer på lagringsstabiliteten av industrifisk tilsatt forskjellige konsentrasjoner av KDF løs-ninger med propylgallat og askorbinsyre. Lagringsstabiliteten av fisk ble bestemt ved å analysere utviklingen av totalt flyktig basisk nitrogen (TVB-N). A pilot-scale experiment was carried out to investigate the effect of different temperatures on the storage stability of industrial fish added with different concentrations of KDF solutions with propyl gallate and ascorbic acid. The storage stability of fish was determined by analyzing the development of total volatile basic nitrogen (TVB-N).
Totalt 6 beholdere (3 liter med lokk) ble hver tilsatt 2,5 kg lodde. Lodden hadde vært frosset før eksperimentet og var av god kvalitet (TVB-N - 7.7 mg/100 g fisk). Fiskebe-holderne ble lagret ved tre forskjellige temperaturer, 1,5, 5,6 og 7,8 °C. To beholdere ble lagret ved hver temperatur, en tilsatt 1,4 vekt % KDF (30 vekt % løsning i vann) med 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre og den andre uten tilsats av A total of 6 containers (3 liters with lids) were each added with 2.5 kg of solder. The capelin had been frozen before the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish). The fish containers were stored at three different temperatures, 1.5, 5.6 and 7.8 °C. Two containers were stored at each temperature, one supplemented with 1.4 wt% KDF (30 wt% solution in water) with 0.5 wt% propyl gallate and 0.5 wt% ascorbic acid and the other without the addition of
KDF løsning. Temperaturen ble registrert under eksperimentet og TVB-N ble analysert. KDF solution. The temperature was recorded during the experiment and the TVB-N was analyzed.
TVB-N utviklingen er vist i Fig. 7. Som kan sees fra Figuren gjør høyere temperatur at TVB-N utviklingen øker i begge beholderne tilsatt KDF løsning omfattende propylgallat og askorbinsyre og kontrollen. Ved alle temperaturene var TVB-N utviklingen i beholderne tilsatt KDF løsning med antioksidant og korrosjonsinhibitor lavere enn TVB-N utviklingen i kontrollprøvene. Ved lagring ved 1,5 °C var TVB-N utviklingen i prøvene omfattende KDF løsning med propylgallat og askorbinsyre bare omtrent 40 mg/100 g etter 30 dagers lagring, mens den tilsvarende lagringsperiode for kontrollen var 9 dager. Ved 7,8 °C var lagringsperioden henholdsvis 16 dager og 5,5 dager. The TVB-N development is shown in Fig. 7. As can be seen from the figure, higher temperature increases the TVB-N development in both containers with added KDF solution comprising propyl gallate and ascorbic acid and the control. At all temperatures, the TVB-N development in the containers with added KDF solution with antioxidant and corrosion inhibitor was lower than the TVB-N development in the control samples. When stored at 1.5 °C, the TVB-N development in the samples comprising KDF solution with propyl gallate and ascorbic acid was only about 40 mg/100 g after 30 days of storage, while the corresponding storage period for the control was 9 days. At 7.8 °C the storage period was 16 days and 5.5 days respectively.
Eksempel 9 Example 9
Et eksperiment i pilotskala ble utført for å undersøke effekten av forskjellige konsentrasjoner av KDF løsninger omfattende propylgallat og askorbinsyre på lagringsstabiliteten av industrifisk. Lagringsstabiliteten av fisk ble bestemt ved å analysere utviklingen av totalt flyktig basisk nitrogen (TVB-N). A pilot-scale experiment was carried out to investigate the effect of different concentrations of KDF solutions comprising propyl gallate and ascorbic acid on the storage stability of industrial fish. The storage stability of fish was determined by analyzing the development of total volatile basic nitrogen (TVB-N).
Totalt 4 beholdere (3 liter med lokk) ble hver tilsatt 2,5 kg lodde. Lodden hadde vært frosset før eksperimentet og var av god kvalitet (TVB-N - 7.7 mg/100 g fisk). Fisken i beholderne ble tilsatt tre forskjellige konsentrasjoner, 1,0,1,4 og 1,8 vekt % KDF løs-ning (30 vekt % løsning i vann) med propylgallat (0,5 vekt %) og askorbinsyre (0,5 vekt %). En beholder ble beholdt som kontroll og ikke tilsatt KDF løsning omfattende propylgallat og askorbinsyre. Beholderne ble lagret ved 5,6 °C. A total of 4 containers (3 liters with lids) were each added with 2.5 kg of solder. The capelin had been frozen before the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish). Three different concentrations were added to the fish in the containers, 1.0, 1.4 and 1.8% by weight KDF solution (30% by weight solution in water) with propyl gallate (0.5% by weight) and ascorbic acid (0.5% by weight %). One container was kept as a control and no KDF solution containing propyl gallate and ascorbic acid was added. The containers were stored at 5.6 °C.
TVB-N utviklingen er vist i Fig. 8. Tilsats av KDF løsning omfattende propylgallat og askorbinsyre ble funnet å redusere TVB-N utviklingen sammenlignet med kontrollprø-ven uten tilsats av KDF løsning omfattende propylgallat og askorbinsyre. Uten tilsats av propylgallat til KDF løsningen var det en rask økning i TVB-N utviklingen etter 4 dager. Da en konsentrasjon på 1 vekt % KDF løsning (30 vekt % løsning i vann) med propylgallat og askorbinsyre ble tilsatt fisken var det en rask økning i TVB-N utviklingen etter omtrent 9 dagers lagring. Med tilsats av en konsentrasjon på 1,4 vekt % kunne fisken lagres i 14 dager før det var en betydelig økning i TVB-N utviklingen. Med 1,8 vekt % tilsatt kunne fisken lagres i over 20 dager uten betydelig økning i TVB-N utviklingen. TVB-N development is shown in Fig. 8. Addition of KDF solution comprising propyl gallate and ascorbic acid was found to reduce TVB-N development compared to the control sample without addition of KDF solution comprising propyl gallate and ascorbic acid. Without the addition of propyl gallate to the KDF solution, there was a rapid increase in TVB-N development after 4 days. When a concentration of 1 wt% KDF solution (30 wt% solution in water) with propyl gallate and ascorbic acid was added to the fish, there was a rapid increase in TVB-N development after approximately 9 days of storage. With the addition of a concentration of 1.4% by weight, the fish could be stored for 14 days before there was a significant increase in TVB-N development. With 1.8% by weight added, the fish could be stored for over 20 days without a significant increase in TVB-N development.
Eksempel 10 Example 10
Effekten av å tilsette propylgallat for å forhindre oksidasjon av lipidfraksjonen av fisk og biprodukter av fisk ble undersøkt i et laboratorieeksperiment. The effect of adding propyl gallate to prevent oxidation of the lipid fraction of fish and fish by-products was investigated in a laboratory experiment.
Biprodukter av sild ble tilsatt 1,5 vekt % av en 30 vekt % KDF løsning eller en 30 vekt % KDF løsning med 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre. Løsningene ble blandet med fisken og lagret ved 5 °C. Prøver ble tatt ut etter 0,6, 9 og 12 dager. Prøvene ble tatt ut for analyser av TVB-N og oljekvalitet. Da TVB-N verdien oversteg 80 mg/100 g fisk ble prøvene forkastet fra eksperimentet på grunn av den høye graden av nedbrytning. Prøvene ble kokt i en autoklav i 45 minutter, og så sentrifugert i 5 minutter og oljen hentet ut. Prøvene ble spylt med nitrogen og lagret ved -80 °C inntil de ble analysert. Oljekvaliteten ble bestemt ved å analysere peroksid (POV) og p-anisidin (p-AV) verdien. Totox ble så beregnet som 2x POV + p-AV. By-products of herring were added 1.5% by weight of a 30% by weight KDF solution or a 30% by weight KDF solution with 0.5% by weight propyl gallate and 0.5% by weight ascorbic acid. The solutions were mixed with the fish and stored at 5 °C. Samples were taken after 0.6, 9 and 12 days. The samples were taken for analyzes of TVB-N and oil quality. When the TVB-N value exceeded 80 mg/100 g fish, the samples were discarded from the experiment due to the high degree of degradation. The samples were boiled in an autoclave for 45 minutes, then centrifuged for 5 minutes and the oil extracted. The samples were flushed with nitrogen and stored at -80 °C until analyzed. The oil quality was determined by analyzing the peroxide (POV) and p-anisidine (p-AV) value. Totox was then calculated as 2x POV + p-AV.
Resultatene av analysene er vist i Fig. 9. En positiv effekt av å tilsette propylgallat og askorbinsyre ble observert ved alle prøvetakingene. Etter 9 dager var totox for oljen fra fisk behandlet med 1,5 vekt % av en 30 vekt % KDF løsing omfattende 0,5 vekt % propylgallat og 0,5 vekt % askorbinsyre rett over 3 sammenlignet med over 9 i prøven uten antioksidant, og etter 12 dager var totox 3,6 i gruppen tilsatt antioksidant. The results of the analyzes are shown in Fig. 9. A positive effect of adding propyl gallate and ascorbic acid was observed at all samplings. After 9 days, the totox for the oil from fish treated with 1.5 wt% of a 30 wt% KDF solution comprising 0.5 wt% propyl gallate and 0.5 wt% ascorbic acid was just over 3 compared to over 9 in the sample without antioxidant, and after 12 days, totox was 3.6 in the antioxidant-added group.
Konserveringsmiddelet ifølge foreliggende oppfinnelse gir en forlenget lagringsperiode for produkter behandlet med nevnte konserveringsmiddel. Den tilsatte korrosjonsinhibitoren hindrer at antioksidanten feller ut over tid og reduserer også korrosjon av konserveringsmiddelet. The preservative according to the present invention provides an extended storage period for products treated with said preservative. The added corrosion inhibitor prevents the antioxidant from falling out over time and also reduces corrosion of the preservative.
Produktet ifølge oppfinnelsen er særlig velegnet for konservering av fisk, fiskeprodukter og fiskebiprodukter. Antioksidanten reduserer TVB-N utviklingen og forhindrer oksidasjon i oljen under lagring av fiskeproduktene. The product according to the invention is particularly suitable for preserving fish, fish products and fish by-products. The antioxidant reduces TVB-N development and prevents oxidation in the oil during storage of fish products.
Claims (6)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO20025472A NO317162B1 (en) | 2002-11-15 | 2002-11-15 | Stable preservative |
| GB0508679A GB2409623B (en) | 2002-11-15 | 2003-10-22 | Preservative agent |
| AU2003282633A AU2003282633A1 (en) | 2002-11-15 | 2003-10-22 | Preservative agent |
| PCT/NO2003/000349 WO2004045317A1 (en) | 2002-11-15 | 2003-10-22 | Preservative agent |
| PE2003001130A PE20040546A1 (en) | 2002-11-15 | 2003-11-07 | PRESERVING AGENT |
| DK200500683A DK178350B1 (en) | 2002-11-15 | 2005-05-11 | Preservative |
| IS7865A IS2316B (en) | 2002-11-15 | 2005-05-25 | Stable preservative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO20025472A NO317162B1 (en) | 2002-11-15 | 2002-11-15 | Stable preservative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO20025472D0 NO20025472D0 (en) | 2002-11-15 |
| NO317162B1 true NO317162B1 (en) | 2004-08-30 |
Family
ID=19914180
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO20025472A NO317162B1 (en) | 2002-11-15 | 2002-11-15 | Stable preservative |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU2003282633A1 (en) |
| DK (1) | DK178350B1 (en) |
| GB (1) | GB2409623B (en) |
| IS (1) | IS2316B (en) |
| NO (1) | NO317162B1 (en) |
| PE (1) | PE20040546A1 (en) |
| WO (1) | WO2004045317A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO321226B1 (en) * | 2004-05-12 | 2006-04-10 | Yara Int Asa | Process for Stabilizing Ethoxyquin in Aqueous Formic Acid Solution, Aqueous Formic Acid Solution comprising Ethoxyquin as Antioxidant, and Use for Stabilizing Ethoxyquin |
| CN104095027B (en) * | 2013-04-02 | 2016-03-02 | 浙江海洋学院 | Tuna muscle protect look special agent and color protecting method |
| US11470868B2 (en) | 2019-11-08 | 2022-10-18 | Héctor Rodrigo Latorre Salas | Biotechnological composition and its application at a stick water evaporation plant during the fish meal and oil manufacturing process, aimed to avoid increase of nitrogen volatile compounds and to reduce the viscosity of stick water concentrate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO300192B1 (en) * | 1995-08-07 | 1997-04-28 | Sildolje & Sildemelind Forsk | Process for the cooling and preservation of fish and product of fish treated according to the method |
| NO309796B1 (en) * | 1999-03-08 | 2001-04-02 | Norsk Hydro As | A new ensiling agent, method of preparing this ensiling agent and its use |
| AU2621201A (en) * | 1999-11-01 | 2001-05-14 | University Of Massachusetts | Method for selective delivery of lipid-soluble antioxidants into the polar lipidfraction of a food product |
-
2002
- 2002-11-15 NO NO20025472A patent/NO317162B1/en not_active IP Right Cessation
-
2003
- 2003-10-22 WO PCT/NO2003/000349 patent/WO2004045317A1/en not_active Application Discontinuation
- 2003-10-22 GB GB0508679A patent/GB2409623B/en not_active Expired - Fee Related
- 2003-10-22 AU AU2003282633A patent/AU2003282633A1/en not_active Abandoned
- 2003-11-07 PE PE2003001130A patent/PE20040546A1/en active IP Right Grant
-
2005
- 2005-05-11 DK DK200500683A patent/DK178350B1/en not_active IP Right Cessation
- 2005-05-25 IS IS7865A patent/IS2316B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2409623B (en) | 2006-07-12 |
| DK200500683A (en) | 2005-05-11 |
| IS2316B (en) | 2007-11-15 |
| PE20040546A1 (en) | 2004-08-26 |
| NO20025472D0 (en) | 2002-11-15 |
| GB0508679D0 (en) | 2005-06-08 |
| AU2003282633A1 (en) | 2004-06-15 |
| IS7865A (en) | 2005-05-25 |
| GB2409623A (en) | 2005-07-06 |
| DK178350B1 (en) | 2016-01-04 |
| WO2004045317A1 (en) | 2004-06-03 |
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