CN112715743B - Method for recovering protein and fish oil in minced fillet rinsing water and reducing COD (chemical oxygen demand) - Google Patents

Method for recovering protein and fish oil in minced fillet rinsing water and reducing COD (chemical oxygen demand) Download PDF

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CN112715743B
CN112715743B CN201910975684.XA CN201910975684A CN112715743B CN 112715743 B CN112715743 B CN 112715743B CN 201910975684 A CN201910975684 A CN 201910975684A CN 112715743 B CN112715743 B CN 112715743B
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protein
fish oil
rinsing water
minced fillet
water
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CN112715743A (en
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吴正奇
陈小强
李倩
吴龙
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Hubei University of Technology
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23JPROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J1/00Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
    • A23J1/04Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from fish or other sea animals
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B13/00Recovery of fats, fatty oils or fatty acids from waste materials
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/74Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Edible Oils And Fats (AREA)

Abstract

The invention discloses a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD, which comprises the following steps: the method comprises the following steps of alkalization, air blowing and stirring dissolution: alkalizing the minced fillet rinsing water, blowing air, and stirring to obtain protein-denatured alkalized-oxidized minced fillet rinsing water; adjusting pH and settling: adjusting the pH value and settling of the protein-denatured alkalized-oxidized minced fillet rinsing water to obtain a settled supernatant and a protein-fish oil settled precipitate; separating: precipitating protein-fish oil, separating liquid from solid, dehydrating, and separating centrifugal supernatant to obtain recovered minced fillet rinsing water protein and fish oil; and (4) combining the settled supernatant and the centrifuged supernatant to obtain the rinsing water with the protein and fish oil removed and the COD content reduced. The method has low cost and simple treatment process, and can recover edible protein and fish oil to increase economic benefit and reduce the difficulty and cost of sewage treatment of minced fillet rinse water.

Description

Method for recovering protein and fish oil in minced fillet rinsing water and reducing COD (chemical oxygen demand)
Technical Field
The invention belongs to the technical field of aquatic product processing, and particularly relates to a method for recovering edible protein and fish oil from minced fillet rinsing water and reducing COD (chemical oxygen demand) of the minced fillet rinsing water, which is suitable for recovering the protein and the fish oil from fresh water minced fillet and seawater minced fillet rinsing water, and is suitable for subsequent processing and comprehensive utilization, and is also a necessary procedure of pretreatment of the fresh water minced fillet and seawater minced fillet rinsing water as sewage to enter a sewage treatment plant and a sewage treatment process of the fresh water minced fillet and seawater minced fillet rinsing water.
Background
Minced fillet, which is a minced fish product with pure white appearance and no bone spurs prepared by the working procedures of killing freshwater fish or seawater fish, removing internal organs, cleaning, collecting meat, rinsing, dehydrating, finely filtering, squeezing and the like, wherein the minced fillet can be prepared into frozen minced fillet for long-term storage and sale; frozen minced fillet is an essential raw material for producing minced fillet products such as fish balls, fish cakes, sausages, crab sticks and the like in the food industry. With the acceleration of life rhythm and socialization of family kitchens, the social demand of minced fillet is more and more great, and the seawater fish and the fish are used in Jiangsu, Fujian, Guangdong and Hubei, Sichuan and Jiangxi in the southeast and coastal areas of ChinaA factory for producing minced fillet by freshwater fish. In the production process of minced fillet, rinsing is the most important and indispensable process for determining the quality of the minced fillet, the aim of rinsing is to wash out water-soluble proteins, hemoglobin (blood color), fish oil and other components which influence the elasticity and color of the minced fillet product in fish muscle tissues by using water, so that the quality of the minced fillet is improved, and a large amount of minced fillet rinsing water is generated in the rinsing of the minced fillet. The minced fish rinsing water contains water-soluble protein 30% of fish protein, enzymes capable of hydrolyzing protein, tiny minced fish particles (water-insoluble protein), fish oil and hemoglobin, and has turbid appearance, floating fat and fishy smell. At present, minced fillet rinsing water is used as sewage to enter a sewage treatment plant for biochemical treatment and then is discharged, and the COD of the minced fillet rinsing water is 10000-25000 mgO 2The oil-in-water emulsion has the advantages of high treatment difficulty, high cost and difficulty in meeting the discharge requirement due to red blood and grease. In view of this, a new technology capable of recovering edible protein and fish oil to increase economic benefits and reducing the difficulty and cost of wastewater treatment of surimi rinsing water is urgently needed to promote the efficient, sustained and robust development of surimi processing industry.
The existing method for recovering water-soluble protein in minced fillet rinsing water has the following defects: 1. the recovery of protein and fish oil in the minced fillet rinsing water is insufficient, and the recovery rate is low; 2. the protein and the fish oil which are recovered due to the use of the flocculating agent cannot be eaten, so that the economy is poor; 3. the surimi rinsing water after the recovery of protein and fish oil still presents a blood red appearance, has small COD reduction rate, unclear and transparent appearance, large colorless treatment difficulty and high cost. Therefore, the continuous research on the treatment technology of the minced fillet rinsing water can fully utilize resources, reduce pollution and provide economic benefits, and has important social, economic and practical significance.
Disclosure of Invention
Aiming at the problems of insufficient utilization of minced fillet rinsing water in processing and high COD value of the minced fillet rinsing water, the invention provides a method for recovering edible protein and fish oil from the minced fillet rinsing water and reducing the COD value of the minced fillet rinsing water, the method has low cost, and the recovered minced fillet rinsing water protein and fish oil products have white color, high sanitary safety, edibility and high recovery rate and can be mechanically manufactured; the minced fillet rinsing water after the recovery of the protein and the fish oil has colorless appearance, is clear and transparent, has no floating oil, has low COD and is convenient for sewage treatment.
The technical concept of the invention is as follows: the method comprises the steps of utilizing protease, water-soluble protein and water-insoluble protein in minced fillet rinsing water to generate structure stretching under the alkaline condition, oxidizing sulfhydryl into disulfide bond to generate intermolecular crosslinking agglomeration, precipitating by calcium ions, adsorbing grease and heme by precipitate, providing alkalinity and releasing calcium ions by neutralizing calcium hydroxide after calcium hydroxide is slightly dissolved in water, adding calcium hydroxide into minced fillet rinsing water, stirring for dissolving, alkalizing, blowing air, oxidizing protein sulfhydryl into disulfide bond for denaturation agglomeration, neutralizing and adjusting pH value by acid liquor, combining released calcium ions with protein (enzyme), fatty acid, nucleic acid, phospholipid and the like which are oxidized and denatured into agglomeration to generate protein complex precipitate, adsorbing fish oil and heme by the protein complex precipitate under the stirring condition, separating supernatant and protein-fish oil precipitation liquid after precipitation, and performing solid-liquid separation on the protein-fish oil precipitation liquid, obtaining the recovered minced fillet rinsing water protein and fish oil; and (4) mixing the settled supernatant with the clear liquid obtained by solid-liquid separation to obtain the rinsing water with reduced COD.
In order to achieve the purpose, the invention adopts the following technical measures:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
The method comprises the following steps of alkalization, air blowing and stirring dissolution: taking surimi rinsing water, adding a calcium hydroxide suspension under the condition of stirring until the pH value of the surimi rinsing water is 11.5-13.5, blowing air, and continuously stirring to ensure that protease, water-soluble protein and water-insoluble protein in the surimi rinsing water are fully unfolded in structure, fully oxidized into disulfide bonds by sulfydryl, fully inactivated by protease and fully oxidized and denatured by protein under the conditions of alkalinity and oxygen, thus obtaining the protein-denatured alkalized-oxidized surimi rinsing water for later use.
Preferably, the minced fillet rinsing water is fish killing cleaning water, minced fillet rinsing water or mixed water of the fish killing cleaning water and the minced fillet rinsing water, which are generated by producing minced fillets by using freshwater fish and marine fish as raw materials; the calcium hydroxide is food-grade calcium hydroxide.
The method comprises the following steps of: adjusting the pH value of the alkalized and oxidized minced fillet rinsing water subjected to protein denaturation obtained in the step to 7.5-8.5 by using an acid solution under the condition of stirring, fully combining calcium ions released by calcium hydroxide with denatured proteins, enzyme proteins, fatty acids, nucleic acids, phospholipids and the like in the minced fillet rinsing water to generate a protein compound precipitate, and continuously stirring to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for precipitation, fully precipitating protein complex-fish oil particles, and decanting the supernatant A to obtain protein-fish oil precipitation solution.
Preferably, the acid solution is food-grade hydrochloric acid.
Performing solid-liquid separation: dehydrating the protein-fish oil sedimentation precipitation liquid obtained in the step II by using a solid-liquid separation method, and separating clear liquid B with protein and fish oil removed to obtain the recovered surimi rinsing water protein and fish oil; and combining the clear liquid A and the clear liquid B to obtain rinsing water with reduced COD content of protein and fish oil removed, and treating in a sewage treatment plant.
The solid-liquid separation method is a centrifugal separation method, a filtration method and a bag filtration method which are commonly used in industry.
Preferably, the solid-liquid separation method is a centrifugal separation method and a bag filtration method which are commonly used in industry.
Compared with the prior art, the method has the advantages and beneficial effects that:
1. the invention mainly provides alkaline conditions after calcium hydroxide is slightly dissolved in water and oxidation conditions provided by air blowing, so that protease, water-soluble protein and water-insoluble protein in minced fillet rinsing water are fully unfolded in structure, sulfhydryl is fully oxidized into disulfide bonds, protease is fully inactivated and protein is fully oxidized and denatured in the presence of alkaline and oxygen, and the technical problems and difficulties that the protease is difficult to inactivate and is used for continuously hydrolyzing the protein in the minced fillet rinsing water into small molecules and peptide substances which cannot be precipitated, the protein is difficult to fully denature and is difficult to agglomerate molecules and the like are solved; calcium ions released by the dissolved calcium hydroxide are combined with protein, enzyme protein, fatty acid, nucleic acid, phospholipid and the like which are oxidized and denatured into clusters to generate protein compound precipitate by neutralizing and adjusting the pH value, so that the technical problem and difficulty of full precipitation of the protein in the minced fillet rinsing water are solved; the fish oil, the hemoglobin and the heme (myoglobin and hemoglobin) are adsorbed by the protein compound sediment, so that the technical problems and difficulties of oil separation and red blood removal in minced fillet rinsing water are solved. The method mainly achieves the technical effects that the protease in the minced fillet rinsing water is completely inactivated without hydrolyzing the protein in the minced fillet rinsing water into micromolecule and peptide substances which cannot be precipitated, the protein is fully precipitated, the fish oil and the blood red substances are fully adsorbed, the recovered protein and the fish oil are edible, the COD (chemical oxygen demand) of the treated minced fillet rinsing water is greatly reduced, no fish oil floats, the appearance is colorless, the surimi rinsing water is clear and transparent, the sewage is convenient to treat, the edible protein and the fish oil are recovered, the economic benefit is increased, and the sewage treatment difficulty and cost of the minced fillet rinsing water are reduced through the technical means. Compared with the prior art, the method has the advantages that the isoelectric point is adjusted through pH or a flocculating agent is used in the prior art, the protease is not inactivated and the protein is not fully denatured, so that only part of the protein and the fish oil in the minced fillet rinsing water can be recovered, the recovered protein and the fish oil cannot be eaten, the treated minced fillet rinsing water is reddish in blood, and the COD (chemical oxygen demand) is not obviously reduced; the invention realizes the technical breakthrough that protease in the minced fillet rinsing water is inactivated and denatured, protein and fish oil are completely recovered, the recovered protein and fish oil are edible, the treated minced fillet rinsing water is colorless, clear and transparent, COD is remarkably reduced, and sewage treatment is facilitated.
2. Through the technical treatment of the invention, the recovery rate of protein in the minced fillet rinsing water is not less than 95%, the recovery rate of fish oil is 100%, the decoloration rate of the minced fillet rinsing water before and after treatment is 100%, and the COD reduction rate is more than 80%, so that the sewage treatment is facilitated, and the dual purposes of recycling edible protein and fish oil, increasing economic benefits, and reducing the sewage treatment difficulty and cost of the minced fillet rinsing water are achieved. Through determination, the protein and the fish oil recovered from the minced fillet rinsing water are edible, and the physicochemical index and the microbial index both meet the requirements of the national relevant standard GB/T36187-2018; the processed minced fillet rinsing water is colorless, clear and transparent in appearance.
3. The method has low cost and simple and convenient treatment process, increases economic benefit by recycling edible protein and fish oil, reduces the difficulty and cost for treating the sewage of the minced fillet rinsing water, and has white color, high sanitary safety, edibility and high recovery rate of the recycled minced fillet rinsing water protein and fish oil products; the minced fillet rinsing water after the recovery of the protein and the fish oil has colorless appearance, is clear and transparent, has no floating oil, has low COD, is convenient for sewage treatment, can be produced mechanically, and can adapt to large-scale and small-scale production.
Drawings
FIG. 1 is a process flow diagram of a process for recovering protein and fish oil from surimi rinse water and reducing COD.
Detailed Description
The applicant shall now describe the process of the present invention in further detail with reference to specific examples.
Example 1:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. basification, air sparging and dissolution with stirring: taking the COD as 15000mgO2Adding 5 kilograms of/L minced fillet rinsing water, adding 5.5 percent by mass of calcium hydroxide suspension under the condition of stirring until the pH of the minced fillet rinsing water is 12.5, and continuously stirring for 2.5 hours while blowing air to fully dissolve the calcium hydroxide, fully oxidize the sulfhydryl of the protein into disulfide bonds, fully inactivate protease and fully oxidize and denature the protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8 by using a hydrochloric acid solution with the mass percentage concentration of 5.5 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 2.5 hours to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 3.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 0.25 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 2028mgO2And the/L colorless transparent rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 74.8 percent, the protein (dry weight, calculated by Nx 6.25) content is 84 percent, the fish oil content is 11 percent, the ash content is less than or equal to 5 percent, and the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 2028mgO2The COD reduction rate was 86.48%.
Example 2:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 20000mgO285 kg of/L minced fillet rinsing water, adding a calcium hydroxide suspension with the mass percentage concentration of 4% under the condition of stirring until the pH value of the minced fillet rinsing water is 13, and continuously stirring for 1.5 hours while blowing air to fully dissolve the calcium hydroxide, fully oxidize protein sulfydryl into disulfide bonds, fully inactivate protease and fully oxidize and denature protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8.5 by using a hydrochloric acid solution with the mass percentage concentration of 4 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 0.5 hour to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 2.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 5.95 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with COD content of protein and fish oil reduced to 1930mgO2And (4) introducing the/L colorless transparent rinsing water into a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 97.1 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 72.8 percent, the protein (dry weight, calculated by Nx 6.25) content is 85.1 percent, the fish oil content is 10 percent, the ash content is less than or equal to 4.9 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of the protein and the fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 1930mgO2The COD reduction rate was 90.35%.
Example 3:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 21000mgO2156 kg of minced fillet rinsing water, adding 3 percent by weight of calcium hydroxide suspension under the condition of stirring until the pH value of the minced fillet rinsing water is 13.5, and blowing inAnd continuously stirring for 0.5 hour while air is used, so that calcium hydroxide is fully dissolved, sulfydryl of the protein is fully oxidized into a disulfide bond, protease is fully inactivated, and the protein is fully oxidized and denatured, and the protein-denatured alkalized-oxidized minced fillet rinsing water is obtained for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalized-oxidized minced fillet rinsing water with denatured protein obtained in the step 1 to 7.5 by using a hydrochloric acid solution with the mass percentage concentration of 3 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein complex precipitates, and continuing stirring for 4.5 hours to enable the protein complex precipitates to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 5.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 11.5 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein and fish oil removed and COD content reduced to 1890mgO2And (4) introducing the/L colorless transparent rinsing water into a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 96.8 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 73.6 percent, the protein (dry weight, calculated by Nx 6.25) content is 85.4 percent, the fish oil content is 9.6 percent, the ash content is less than or equal to 5 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 1890mgO2The COD reduction rate was 91%.
Example 4:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: 19000 as mgO2283 kg of/L minced fillet rinsing water, adding 2 percent by mass of calcium hydroxide suspension under the condition of stirring until the pH of the minced fillet rinsing water is 12, and continuously stirring for 3.5 hours while blowing air to fully dissolve the calcium hydroxide, fully oxidize protein sulfydryl into disulfide bonds, fully inactivate protease and fully oxidize and denature protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8.0 by using a hydrochloric acid solution with the mass percentage concentration of 2 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 3.5 hours to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 3 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 18.7 kg of recycled surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the mixture with the COD content of the protein-removed and fish oil reduced to 2100mgO2And the/L colorless transparent rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. The recovered protein and fish oil product has water content of 76.3%, protein content (dry weight, calculated by Nx 6.25) of 82.7%, fish oil content of 12.3%, ash content less than or equal to 5%, and physical and chemical indexes and microbial indexes meeting the relevant national standardThe requirements of GB/T36187-2018); the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 2100mgO2The COD reduction rate was 88.9%.
Example 5:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 14000mgO2328 kg of/L minced fillet rinsing water, adding 1 percent by mass of calcium hydroxide suspension under the condition of stirring until the pH value of the minced fillet rinsing water is 11.5, and continuously stirring for 4.5 hours while blowing air to fully dissolve the calcium hydroxide, fully oxidize protein sulfydryl into disulfide bonds, fully inactivate protease and fully oxidize and denature protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8.5 by using a hydrochloric acid solution with the mass percentage concentration of 1%, fully combining calcium ions released by calcium hydroxide with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuously stirring for 1 hour to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 1.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 15.1 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 2120mgO2And the/L colorless transparent rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95.2 percent, and the recovery rate of fish oil is 100 percent; measured, rinsing water from surimiThe recovered protein and fish oil product is white in color, edible, and has the smell and taste of minced fillet. In the recovered protein and fish oil products, the water content is 77.1 percent, the protein (dry weight, calculated by Nx 6.25) content is 84.5 percent, the fish oil content is 10.5 percent, the ash content is less than or equal to 5 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 2120mgO2The COD reduction rate was 84.86%.
Example 6:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking the COD as 13000mgO2458 kg of/L minced fillet rinsing water, adding a calcium hydroxide suspension with the mass percentage concentration of 6.5% under the condition of stirring until the pH value of the minced fillet rinsing water is 12.5, and continuously stirring for 2.5 hours while blowing air to fully dissolve the calcium hydroxide, fully oxidize the sulfhydryl of the protein into disulfide bonds, fully inactivate protease and fully oxidize and denature the protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8 by using a hydrochloric acid solution with the mass percentage concentration of 6.5 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 2.5 hours to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 3.5 hr to allow protein complex-fish oil granule to settle sufficiently, and collecting supernatant A containing deproteinized and fish oil to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 19.2 kg of recycled surimi rinsing water protein and fish oil; clear solution AMixing with clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 2000mgO2And the/L rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95.8 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 74.3 percent, the protein (dry weight, calculated by Nx 6.25) content is 85.7 percent, the fish oil content is 9.3 percent, the ash content is less than or equal to 5 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent, has no floating oil and COD of 2000mgO2The COD reduction rate was 84.61%.
Example 7:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 12000mgO2567 kg of/L minced fillet rinsing water, adding 7.5 percent zinc hydroxide suspension by mass percentage concentration under the condition of stirring until the pH value of the minced fillet rinsing water is 13, and continuing stirring for 1.5 hours while blowing air to fully dissolve calcium hydroxide, fully oxidize sulfhydryl of protein into disulfide bond, fully inactivate protease and fully oxidize and denature protein to obtain alkalized-oxidized minced fillet rinsing water with denatured protein for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8.5 by using a hydrochloric acid solution with the mass percentage concentration of 7.5 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 1.5 hours to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 2.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 21.6 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 1900mgO2And the/L rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 96.3 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 72 percent, the protein (dry weight, calculated by Nx 6.25) content is 86 percent, the fish oil content is 9 percent, the ash content is less than or equal to 5 percent, and the physicochemical index and the microbial index both meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent, has no floating oil and COD of 1900mgO2The COD reduction rate was 84.17%.
Example 8:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 11000mgO2628 kg of/L minced fillet rinsing water, adding calcium hydroxide suspension with the mass percentage concentration of 8.5% under the condition of stirring until the pH value of the minced fillet rinsing water is 13.5, and continuously stirring for 0.5 hour while blowing air to fully dissolve the calcium hydroxide, fully oxidize the sulfhydryl of the protein into disulfide bonds, fully inactivate protease and fully oxidize and denature the protein to obtain the alkalized-oxidized minced fillet rinsing water with denatured protein for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 7.5 by using a hydrochloric acid solution with the mass percentage concentration of 8.5 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 0.5 hour to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 1.5 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 21.4 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 1850mgO2And the/L rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 96.7 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 72 percent, the protein (dry weight, calculated by Nx 6.25) content is 84.5 percent, the fish oil content is not less than 9.5 percent, the ash content is not less than 5 percent, and the physical and chemical indexes and the microorganism indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of the protein and the fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 1850mgO2The COD reduction rate was 83.18%.
Example 9:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 10000mgO2771 kg of/L minced fillet rinsing water, adding 10 percent by mass of calcium hydroxide suspension under the condition of stirring until the pH of the minced fillet rinsing water is 13, continuously stirring for 1.5 hours while blowing air to fully dissolve calcium hydroxide, fully oxidize protein sulfydryl into disulfide bonds, fully inactivate protease and fully oxidize and denature protein to obtain alkalized-oxidized minced fillet rinsing water with denatured protein for later use。
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalized-oxidized minced fillet rinsing water with denatured protein obtained in the step 1 to 8.5 by using a hydrochloric acid solution with the mass percentage concentration of 10 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein complex precipitates, and continuing stirring for 3.5 hours to enable the protein complex precipitates to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for 2 hr to allow protein complex-fish oil granule to settle, and decanting the supernatant A to obtain protein-fish oil settling solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 23.1 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 1905mgO2And the/L rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95.9 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 75.6 percent, the protein (dry weight, calculated by Nx 6.25) content is 82.8 percent, the fish oil content is 12.2 percent, the ash content is less than or equal to 5 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of the protein and the fish oil has colorless appearance, is clear and transparent and has no floating oil, and the COD is 1905mgO2The COD reduction rate was 80.95%.
Example 10:
a method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
1. Basification, air sparging and dissolution with stirring: taking COD as 18000mgO2859 kg of/L minced fillet rinsing water, and 5 percent of the minced fillet rinsing water by mass percentage under the condition of stirringAnd (3) stirring the suspension until the pH of the minced fillet rinsing water is 13.1 while blowing air for 1 hour to fully dissolve the calcium hydroxide, fully oxidize the sulfhydryl of the protein into disulfide bonds, fully inactivate the protease and fully oxidize and denature the protein to obtain the protein-denatured alkalized-oxidized minced fillet rinsing water for later use.
2. Neutralization, pH adjustment and sedimentation: under the condition of stirring, adjusting the pH value of the alkalization-oxidation minced fillet rinsing water with denatured protein obtained in the step 1 to 8.3 by using a hydrochloric acid solution with the mass percentage concentration of 5 percent, enabling calcium ions released by calcium hydroxide to be fully combined with denatured protein (enzyme), fatty acid, nucleic acid, phospholipid and the like in the minced fillet rinsing water to generate protein compound precipitate, and continuing stirring for 3 hours to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for precipitation for 4 hr to allow protein complex-fish oil granule to fully precipitate, and decanting supernatant A of deproteinized and fish oil to obtain protein-fish oil precipitation solution.
3. Solid-liquid separation: dewatering the protein-fish oil sedimentation precipitation liquid obtained in the step 2 by a solid-liquid separation method, and separating clear liquid B of the protein and the fish oil to obtain 53.3 kg of recovered surimi rinsing water protein and fish oil; mixing the clear liquid A and the clear liquid B to obtain the product with protein removed and fish oil COD content reduced to 1900mgO2And the/L rinsing water enters a sewage treatment plant for treatment.
By the method, the recovery rate of protein in the minced fillet rinsing water is 95.6 percent, and the recovery rate of fish oil is 100 percent; through determination, the protein and fish oil products recovered from the minced fillet rinsing water are white in color, edible and have the smell and taste of the minced fillet. In the recovered protein and fish oil products, the water content is 78.3 percent, the protein (dry weight, calculated by Nx 6.25) content is 83.7 percent, the fish oil content is 11.3 percent, the ash content is less than or equal to 5 percent, and both the physical and chemical indexes and the microbial indexes meet the requirements of the national relevant standard GB/T36187-2018; the minced fillet rinsing water after the recovery of protein and fish oil has colorless appearance, is clear and transparent, has no floating oil and COD of 1900mgO2The COD reduction rate was 89.44%.
The specific embodiments described in this specification are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (4)

1. A method for recovering protein and fish oil in minced fillet rinsing water and reducing COD comprises the following steps:
the method comprises the following steps of alkalization, air blowing and stirring dissolution: taking surimi rinsing water, adding a calcium hydroxide suspension under the condition of stirring until the pH value of the surimi rinsing water is 11.5-13.5, blowing air, and continuously stirring to ensure that protease, water-soluble protein and water-insoluble protein in the surimi rinsing water have fully-stretched structure, fully-oxidized sulfhydryl into disulfide bonds, fully-inactivated protease and fully-oxidized protein in the presence of alkalinity and oxygen to obtain protein-denatured alkalized-oxidized surimi rinsing water for later use;
the method comprises the following steps of: adjusting the pH value of the alkalized and oxidized minced fillet rinsing water subjected to protein denaturation obtained in the step to 7.5-8.5 by using an acid solution under the condition of stirring, fully combining calcium ions released by calcium hydroxide with denatured protein, enzyme protein, fatty acid, nucleic acid and phospholipid in the minced fillet rinsing water to generate a protein compound precipitate, and continuously stirring to enable the protein compound precipitate to adsorb fish oil and heme in the rinsing water; stopping stirring, standing for precipitation to fully precipitate protein complex-fish oil particles, and decanting the supernatant A of deproteinized and fish oil to obtain protein-fish oil precipitation solution;
Performing solid-liquid separation: dehydrating the protein-fish oil sedimentation precipitation liquid obtained in the step II by using a solid-liquid separation method, and separating clear liquid B with protein and fish oil removed to obtain the recovered surimi rinsing water protein and fish oil; and combining the clear liquid A and the clear liquid B to obtain rinsing water with reduced COD content of protein and fish oil removed, and treating in a sewage treatment plant.
2. The method for recovering protein and fish oil and reducing COD in surimi rinse water of claim 1, wherein: the minced fillet rinsing water is fish killing cleaning water, minced fillet rinsing water or mixed water of the fish killing cleaning water and the minced fillet rinsing water, which are produced by producing minced fillets by using freshwater fish and seawater fish as raw materials; the calcium hydroxide is food-grade calcium hydroxide.
3. The method for recovering protein and fish oil and reducing COD in surimi rinse water of claim 1, wherein: the acid solution in the step II is food-grade hydrochloric acid.
4. The method for recovering protein and fish oil and reducing COD in surimi rinse water of claim 1, wherein: and step three, the solid-liquid separation method is a centrifugal separation method, a filtration method and a bag filtration method which are commonly used in industry.
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