CN106509586A - Preparation method of preservative for biomass food - Google Patents

Preparation method of preservative for biomass food Download PDF

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Publication number
CN106509586A
CN106509586A CN201610945110.4A CN201610945110A CN106509586A CN 106509586 A CN106509586 A CN 106509586A CN 201610945110 A CN201610945110 A CN 201610945110A CN 106509586 A CN106509586 A CN 106509586A
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preservative
micro
charcoal
standby
protamine
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吴迪
邹宇帆
张晶
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation 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
    • A23L3/3463Organic compounds; Microorganisms; Enzymes
    • A23L3/3472Compounds of undetermined constitution obtained from animals or plants
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation 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
    • A23L3/358Inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Botany (AREA)
  • Microbiology (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention discloses a preparation method of a preservative for biomass food and belongs to the technical field of food preservative preparations. Clove oil is extracted for a standby application, then the clove oil is mixed with fishbones, propolis and pig manure, the mixture is subjected to a fermentation, micro-organisms are utilized to conduct a mild rotten treatment of the fishbones to enable the surface of the fishbones to be covered with micro-pores, then a protamine concentrate is extracted from herring spermaries, and the protamine concentrate is reacted with the prepared clove oil and micro-porous fishbone charcoal under the action of a coupling agent to prepare the preservative. The clove oil and protamine having broad spectrum bacteriostasis are used as preservative substances, and then the fishbone charcoal with a huge specific surface area is used to absorb the preservative substances, so that the preservative substances are loaded in the internal pores of the micro-porous fishbone charcoal to play protective and slow release effects. Besides, the used raw materials are natural and non-toxic, and the preservative is long in validity period of the preservation, solves the problems that the traditional chemical preservatives are harmful to the human body and the environment, also makes up the defects of short food shelf life caused by the poor preservation effect, and has very excellent application prospects.

Description

A kind of preparation method of biomass food preservative
Technical field
The present invention relates to a kind of preparation method of biomass food preservative, belongs to food preservative preparing technical field.
Background technology
Food preservative is the corrupt medicament of inhibiting substances.Growth i.e. to the microorganism with corrupt substance as metabolism substrate With lasting inhibitory action.It is important that it can suppress most incident Putrefaction in varied situations, particularly one As sterilization functions it is insufficient when still with persistence effect.
China specify using preservative have 30 kinds of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate etc..But It is that, based on chemical preservative, often containing a large amount of harmful materials, such as benzoate may for existing preservative Alimentary toxicosis phenomenon, sorbic acid and potassium sorbate can be caused to be safe preservative generally acknowledged in the world, but Excess free enthalpy also can shadow The balance of human metabolism is rung, also some preservative may cause cancer, cause deformity or cause alimentary toxicosis etc., this Outward, existing preservative antiseptic effect is poor, causes the storage life of food shorter, it is difficult to meet the market demand.
Protamine is find in fish sperm cell a kind of tiny and the simple strong basicity albumen containing homoarginine Matter, it is to bacillus subtilis, bacillus megaterium, bacillus licheniformis, solidification bacillus cereuss, Lactobacillus plantarum, cheese breast bar Bacterium, streptococcus faecalis etc. have compared with high inhibition effect, but unobvious to gram negative bacteria inhibition.Research discovery, milt Albumen can be acted on some protein for being related to nutrition transport or biosynthesis system in cell membrane, make the function of these protein It is impaired, and then suppress the metabolism of cell and make cell death.Antibacterial effect of the protamine in neutral and alkaline medium It is more notable.
Essential oil is contained in the extract of root, bark, seed or fruit of the fragrant plant in the torrid zone, always people's ratio One of natural antiseptic agent interested.Containing eugenol, tannin etc. in Oleum Caryophylli.Research finds that Oleum Caryophylli is to golden yellow Portugal The food such as grape coccus, escherichia coli, yeast, aspergillus niger have broad-spectrum antibacterial to act on, and to thermally-stabilised, its protrusion within 100 DEG C Feature is that Fungistasis are strong.
The content of the invention
The technical problem to be solved:It is poor for current chemical preservative antiseptic effect, and containing a large amount of to people The harmful material of body and environment, causes shelf life storage shorter, the drawbacks of being detrimental to health is eaten for a long time, there is provided Yi Zhongti Take Oleum Caryophylli standby, then by fish spicule, propolis and pig manure mixed fermentation, using microorganism rotten process micro- to fish spicule so as to surface cloth Full small hole, then protamine concentrated solution is extracted from catfish spermary, with standby Oleum Caryophylli and micro- in the presence of coupling agent Hole fish spicule charcoal reaction, is obtained the method for preservative.The present invention using have broad-spectrum antibacterial Oleum Caryophylli and protamine as Preservative substance, then with the fish spicule charcoal with huge specific surface area adsorbing preservative substance so as to it is supported on inside micropore fish spicule charcoal In hole, protection and slow releasing function, and raw materials Nantural non-toxic are played, anti-corrosion effect duration is long, has both solved traditional chemical The preservative problem harmful to human body and environment, compensate for antiseptic effect difference again causes the short defect of shelf life storage, with pole Good application prospect.
To solve above-mentioned technical problem, the present invention using technical scheme as described below is:
(1)Weigh 500~600g Flos Caryophyllis, with grain crusher crush 10~15min after, be placed in distilling flask, by Flos Caryophylli with Distilled water mass ratio is 1:3, distilled water is added in flask, and connects condensing tube, 20~30min of ebuillition of heated collects distillation The oil water mixture for obtaining, is gone in separatory funnel, 20~30min of stratification, isolated upper strata Oleum Caryophylli, standby With;
(2)500~600g fish spicules, 200~300g propolis, 700~800g pig manures and 2~3L deionized waters are weighed respectively, are mixed After be put in ceramic fermentation tank, temperature be 30~40 DEG C, relative air humidity be 60~70% environment under, the micro- corruption of natural fermentation Process 7~9 days, process terminates rear deionized water and rinses 20~30min, obtain the fish spicule after the micro- corruption in surface, put it into charcoal Change in stove, under nitrogen atmosphere, with 200~300 DEG C of temperature 2~3h of carbonization, obtain micropore fish spicule charcoal, it is standby;
(3)300~400g catfish spermaries are weighed, 20~30min is crushed in homogenate in being put into tissue refiner, by the homogenate for obtaining After being the mixing of 0.3mol/L sulphuric acid with concentration, 1~2h of acidolysis reaction, then addition 900~1000mL concentration is in acidolysis thing 0.1mol/L sodium chloride solutions, after 1~3h of stirring reaction, obtain filtrate with 3 layers of filtered through gauze;
(4)It is 1 in mass ratio:3, in above-mentioned filtrate, add mass fraction to be 70% ethanol solution, after 15~20min of stirring, use Centrifuge puts it into rotary evaporation with 2000~3000r/min rotating speed 10~15min of centrifugal treating, isolated supernatant In instrument, concentrated by rotary evaporation obtains catfish protamine concentrated solution to the 1/3 of its original volume;
(5)Count by weight, weigh 20~30 parts of steps(1)Standby Oleum Caryophylli, 30~40 parts of steps(2)Standby micropore Fish spicule charcoal, 50~60 parts of above-mentioned catfish protamine concentrated solutions and 3~5 parts of silane resin acceptor kh-550s, are sequentially placed into reactor In, after 3~5h of stirring reaction at 40~50 DEG C, be filtrated to get filtering residue, with vacuum freeze-drying machine lyophilizing after, obtain final product biomass food Preservative.
The application process of the present invention:Food preservative obtained in the present invention is added into food pack, addition is The 0.2~0.5% of food gross mass, addition is finished, and stands sealing.After testing, food preservative antiseptic effect of the present invention Good, broad spectrum antibacterial is strong, can effectively prevent the growth of the harmful microbes such as bacillus botulinus and breed, extend shelf life storage 10~ 15 days, and the original nutrition of food, local flavor and color and luster can be effectively kept, it is worthy to be popularized and use.
Compared with additive method, Advantageous Effects are the present invention:
(1)Preparation process of the present invention is simple, and gained food preservative has preferable antiseptic effect and stronger anti-microbial property, can Effectively the pathogenic bacterium in suppression food and putrefaction bacteria, extend shelf life storage 10~15 days;
(2)Food preservative safety and environmental protection of the present invention is nontoxic, good stability, to health non-hazardous.
Specific embodiment
500~600g Flos Caryophyllis are weighed first, are crushed after 10~15min with grain crusher, are placed in distilling flask, by fourth Fragrant is 1 with distilled water mass ratio:3, distilled water is added in flask, and connects condensing tube, 20~30min of ebuillition of heated is collected The oil water mixture that distillation is obtained, is gone in separatory funnel, 20~30min of stratification, isolated upper strata Oleum Caryophylli, It is standby;Weigh 500~600g fish spicules, 200~300g propolis, 700~800g pig manures and 2~3L deionized waters again respectively, mix After be put in ceramic fermentation tank, temperature be 30~40 DEG C, relative air humidity be 60~70% environment under, the micro- corruption of natural fermentation Process 7~9 days, process terminates rear deionized water and rinses 20~30min, obtain the fish spicule after the micro- corruption in surface, put it into charcoal Change in stove, under nitrogen atmosphere, with 200~300 DEG C of temperature 2~3h of carbonization, obtain micropore fish spicule charcoal, it is standby;Then weigh 300~400g catfish spermaries, homogenate in being put into tissue refiner crush 20~30min, by the homogenate for obtaining and concentration are After the mixing of 0.3mol/L sulphuric acid, 1~2h of acidolysis reaction, then in acidolysis thing, add 900~1000mL concentration to be 0.1mol/L chlorine Change sodium solution, after 1~3h of stirring reaction, filtrate is obtained with 3 layers of filtered through gauze;It is 1 in mass ratio:3, add in above-mentioned filtrate Mass fraction is 70% ethanol solution, after 15~20min of stirring, with centrifuge with 2000~3000r/min rotating speeds centrifugal treating 10 ~15min, isolated supernatant, in putting it into Rotary Evaporators, concentrated by rotary evaporation obtains catfish fish to the 1/3 of its original volume Protamine concentrated solution;Finally count by weight, weigh 20~30 portions of standby Oleum Caryophyllis, 30~40 parts of standby micropore fish spicules Charcoal, 50~60 parts of above-mentioned catfish protamine concentrated solutions and 3~5 parts of silane resin acceptor kh-550s, are sequentially placed in reactor, At 40~50 DEG C after 3~5h of stirring reaction, be filtrated to get filtering residue, with vacuum freeze-drying machine lyophilizing after, obtain final product biomass food antiseptic Agent.
Example 1
500g Flos Caryophyllis are weighed first, is crushed after 10min with grain crusher, is placed in distilling flask, by Flos Caryophylli and distillation water quality Amount is than being 1:3, distilled water is added in flask, and connects condensing tube, ebuillition of heated 20min, the profit that collection distillation is obtained are mixed Compound, is gone in separatory funnel, stratification 20min, isolated upper strata Oleum Caryophylli, standby;Weigh 500g again respectively Fish spicule, 200g propolis, 700g pig manures and 2L deionized waters, are put into after mixing in ceramic fermentation tank, are 30 DEG C, air phase in temperature It is the micro- rotten process of natural fermentation 7 days under 60% environment to humidity, process terminates rear deionized water and rinses 20min, obtains surface Fish spicule after micro- corruption, puts it in retort, under nitrogen atmosphere, with 200 DEG C of temperature carbonization 2h, obtains micropore fish spicule Charcoal, it is standby;Then 300g catfish spermaries are weighed, homogenate in tissue refiner is put into and is crushed 20min, by the homogenate for obtaining and dense Spend after mixing for 0.3mol/L sulphuric acid, acidolysis reaction 1h, then in acidolysis thing, add 900mL concentration to be that 0.1mol/L Sodium Chloride is molten Liquid, after stirring reaction 1h, obtains filtrate with 3 layers of filtered through gauze;It is 1 in mass ratio:3, mass fraction is added in above-mentioned filtrate For 70% ethanol solution, after stirring 15min, with centrifuge with 2000r/min rotating speed centrifugal treating 10min, isolated supernatant Liquid, in putting it into Rotary Evaporators, concentrated by rotary evaporation obtains catfish protamine concentrated solution to the 1/3 of its original volume;Finally press Parts by weight meter, weighs 20 portions of standby Oleum Caryophyllis, 30 parts of standby micropore fish spicule charcoals, 50 parts of above-mentioned catfish protamine concentrations Liquid and 3 parts of silane resin acceptor kh-550s, are sequentially placed in reactor, after stirring reaction 3h at 40 DEG C, are filtrated to get filtering residue, use After vacuum freeze-drying machine lyophilizing, biomass food preservative is obtained final product.
Food preservative obtained in the present invention is added into food pack, addition for food gross mass 0.2%, Addition is finished, and stands sealing.After testing, food preservative favorable anti-corrosion effect of the present invention, broad spectrum antibacterial are strong, effectively can prevent Only the growth of the harmful microbe such as bacillus botulinus and breeding, extend shelf life storage 10 days, and can effectively keep food original Nutrition, local flavor and color and luster, are worthy to be popularized and use.
Example 2
550g Flos Caryophyllis are weighed first, is crushed after 13min with grain crusher, is placed in distilling flask, by Flos Caryophylli and distillation water quality Amount is than being 1:3, distilled water is added in flask, and connects condensing tube, ebuillition of heated 25min, the profit that collection distillation is obtained are mixed Compound, is gone in separatory funnel, stratification 25min, isolated upper strata Oleum Caryophylli, standby;Weigh 550g again respectively Fish spicule, 250g propolis, 750g pig manures and 3L deionized waters, are put into after mixing in ceramic fermentation tank, are 35 DEG C, air phase in temperature It is the micro- rotten process of natural fermentation 8 days under 65% environment to humidity, process terminates rear deionized water and rinses 25min, obtains surface Fish spicule after micro- corruption, puts it in retort, under nitrogen atmosphere, with 250 DEG C of temperature carbonization 3h, obtains micropore fish spicule Charcoal, it is standby;Then 350g catfish spermaries are weighed, homogenate in tissue refiner is put into and is crushed 25min, by the homogenate for obtaining and dense Spend after mixing for 0.3mol/L sulphuric acid, acidolysis reaction 2h, then in acidolysis thing, add 950mL concentration to be that 0.1mol/L Sodium Chloride is molten Liquid, after stirring reaction 2h, obtains filtrate with 3 layers of filtered through gauze;It is 1 in mass ratio:3, mass fraction is added in above-mentioned filtrate For 70% ethanol solution, after stirring 18min, with centrifuge with 2500r/min rotating speed centrifugal treating 13min, isolated supernatant Liquid, in putting it into Rotary Evaporators, concentrated by rotary evaporation obtains catfish protamine concentrated solution to the 1/3 of its original volume;Finally press Parts by weight meter, weighs 25 portions of standby Oleum Caryophyllis, 35 parts of standby micropore fish spicule charcoals, 55 parts of above-mentioned catfish protamine concentrations Liquid and 4 parts of silane resin acceptor kh-550s, are sequentially placed in reactor, after stirring reaction 4h at 45 DEG C, are filtrated to get filtering residue, use After vacuum freeze-drying machine lyophilizing, biomass food preservative is obtained final product.
Food preservative obtained in the present invention is added into food pack, addition for food gross mass 0.4%, Addition is finished, and stands sealing.After testing, food preservative favorable anti-corrosion effect of the present invention, broad spectrum antibacterial are strong, effectively can prevent Only the growth of the harmful microbe such as bacillus botulinus and breeding, extend shelf life storage 13 days, and can effectively keep food original Nutrition, local flavor and color and luster, are worthy to be popularized and use.
Example 3
600g Flos Caryophyllis are weighed first, is crushed after 15min with grain crusher, is placed in distilling flask, by Flos Caryophylli and distillation water quality Amount is than being 1:3, distilled water is added in flask, and connects condensing tube, ebuillition of heated 30min, the profit that collection distillation is obtained are mixed Compound, is gone in separatory funnel, stratification 30min, isolated upper strata Oleum Caryophylli, standby;Weigh 600g again respectively Fish spicule, 300g propolis, 800g pig manures and 3L deionized waters, are put into after mixing in ceramic fermentation tank, are 40 DEG C, air phase in temperature It is the micro- rotten process of natural fermentation 9 days under 70% environment to humidity, process terminates rear deionized water and rinses 30min, obtains surface Fish spicule after micro- corruption, puts it in retort, under nitrogen atmosphere, with 300 DEG C of temperature carbonization 3h, obtains micropore fish spicule Charcoal, it is standby;Then 400g catfish spermaries are weighed, homogenate in tissue refiner is put into and is crushed 30min, by the homogenate for obtaining and dense Spend after mixing for 0.3mol/L sulphuric acid, acidolysis reaction 2h, then in acidolysis thing, add 1000mL concentration to be 0.1mol/L Sodium Chloride Solution, after stirring reaction 3h, obtains filtrate with 3 layers of filtered through gauze;It is 1 in mass ratio:3, quality point is added in above-mentioned filtrate Number is 70% ethanol solution, after stirring 20min, with centrifuge with 3000r/min rotating speed centrifugal treating 15min, isolated supernatant Liquid, in putting it into Rotary Evaporators, concentrated by rotary evaporation obtains catfish protamine concentrated solution to the 1/3 of its original volume;Finally press Parts by weight meter, weighs 30 portions of standby Oleum Caryophyllis, 40 parts of standby micropore fish spicule charcoals, 60 parts of above-mentioned catfish protamine concentrations Liquid and 5 parts of silane resin acceptor kh-550s, are sequentially placed in reactor, after stirring reaction 5h at 50 DEG C, are filtrated to get filtering residue, use After vacuum freeze-drying machine lyophilizing, biomass food preservative is obtained final product.
Food preservative obtained in the present invention is added into food pack, addition for food gross mass 0.5%, Addition is finished, and stands sealing.After testing, food preservative favorable anti-corrosion effect of the present invention, broad spectrum antibacterial are strong, effectively can prevent Only the growth of the harmful microbe such as bacillus botulinus and breeding, extend shelf life storage 15 days, and can effectively keep food original Nutrition, local flavor and color and luster, are worthy to be popularized and use.

Claims (1)

1. a kind of preparation method of biomass food preservative, it is characterised in that concrete preparation process is:
(1)Weigh 500~600g Flos Caryophyllis, with grain crusher crush 10~15min after, be placed in distilling flask, by Flos Caryophylli with Distilled water mass ratio is 1:3, distilled water is added in flask, and connects condensing tube, 20~30min of ebuillition of heated collects distillation The oil water mixture for obtaining, is gone in separatory funnel, 20~30min of stratification, isolated upper strata Oleum Caryophylli, standby With;
(2)500~600g fish spicules, 200~300g propolis, 700~800g pig manures and 2~3L deionized waters are weighed respectively, are mixed After be put in ceramic fermentation tank, temperature be 30~40 DEG C, relative air humidity be 60~70% environment under, the micro- corruption of natural fermentation Process 7~9 days, process terminates rear deionized water and rinses 20~30min, obtain the fish spicule after the micro- corruption in surface, put it into charcoal Change in stove, under nitrogen atmosphere, with 200~300 DEG C of temperature 2~3h of carbonization, obtain micropore fish spicule charcoal, it is standby;
(3)300~400g catfish spermaries are weighed, 20~30min is crushed in homogenate in being put into tissue refiner, by the homogenate for obtaining After being the mixing of 0.3mol/L sulphuric acid with concentration, 1~2h of acidolysis reaction, then addition 900~1000mL concentration is in acidolysis thing 0.1mol/L sodium chloride solutions, after 1~3h of stirring reaction, obtain filtrate with 3 layers of filtered through gauze;
(4)It is 1 in mass ratio:3, in above-mentioned filtrate, add mass fraction to be 70% ethanol solution, after 15~20min of stirring, use Centrifuge puts it into rotary evaporation with 2000~3000r/min rotating speed 10~15min of centrifugal treating, isolated supernatant In instrument, concentrated by rotary evaporation obtains catfish protamine concentrated solution to the 1/3 of its original volume;
(5)Count by weight, weigh 20~30 parts of steps(1)Standby Oleum Caryophylli, 30~40 parts of steps(2)Standby micropore Fish spicule charcoal, 50~60 parts of above-mentioned catfish protamine concentrated solutions and 3~5 parts of silane resin acceptor kh-550s, are sequentially placed into reactor In, after 3~5h of stirring reaction at 40~50 DEG C, be filtrated to get filtering residue, with vacuum freeze-drying machine lyophilizing after, obtain final product biomass food Preservative.
CN201610945110.4A 2016-11-02 2016-11-02 Preparation method of preservative for biomass food Pending CN106509586A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101755994A (en) * 2008-12-11 2010-06-30 湖州来色生物基因工程有限公司 Preparation method of natural food preservative of protamine
CN103936846A (en) * 2014-04-30 2014-07-23 上海第一生化药业有限公司 Purification method of protamine sulfate
CN104738787A (en) * 2015-04-17 2015-07-01 黄琳 Natural preservative and preparation method thereof
CN105054219A (en) * 2015-09-18 2015-11-18 四川省汇泉罐头食品有限公司 Compound food preservative

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101755994A (en) * 2008-12-11 2010-06-30 湖州来色生物基因工程有限公司 Preparation method of natural food preservative of protamine
CN103936846A (en) * 2014-04-30 2014-07-23 上海第一生化药业有限公司 Purification method of protamine sulfate
CN104738787A (en) * 2015-04-17 2015-07-01 黄琳 Natural preservative and preparation method thereof
CN105054219A (en) * 2015-09-18 2015-11-18 四川省汇泉罐头食品有限公司 Compound food preservative

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