Method for preparing liquid fertilizer from vitamin B12 waste liquid

Abstract

The invention discloses a method for preparing a liquid fertilizer from vitamin B12 waste liquid, and relates to the field of liquid fertilizers. When the liquid fertilizer is prepared, the vitamin B12 waste liquid is filtered and then subjected to alkaline pretreatment, and solid protein and filtrate are obtained through separation; acidifying the filtrate with sulfuric acid, adding potassium hydroxide, and concentrating under reduced pressure to obtain regenerated mixed salt; carrying out flash explosion treatment on the solid protein, and carrying out enzymolysis by using trypsin and subtilisin to obtain a proteolysis solution; urea, formaldehyde and dimethyl hydrogen phosphate are mixed to prepare slow-release phosphorus-nitrogen macromolecules; and uniformly mixing the protein enzymatic hydrolysate, the regenerated mixed salt, fulvic acid, slow-release phosphorus-nitrogen macromolecules and deionized water to obtain the liquid fertilizer. The prepared liquid fertilizer has the advantages of excellent long-term effect, easy absorption and waste liquid utilization rate.

Description

Technical Field

[0001] The present invention relates to the field of liquid fertilizer, in particular to a vitamin B 12 A method for preparing liquid fertilizer from waste liquid. Background Art

[0002] Vitamin B 12 The English name is Vitamin B 12 , its aliases are cobalamin, cyanocobalamin, etc., and its molecular formula is C 63 H 88 CoN 14 O 14 P, molecular weight is 859.1. Vitamin B 12 It is a very special vitamin that is almost completely not found in vegetables. It is only contained in seaweed and seaweed. In addition, vitamin B 12 It is also the only vitamin that contains essential minerals. It is red because it contains cobalt, so it is also called red vitamin. It is one of the few colored vitamins. 12 It has a wide range of physiological effects. It participates in methyl conversion and folic acid metabolism in the body, promotes the formation of lipoproteins in the myelin sheath, maintains the integrity of the functions of the central nervous system and peripheral myelinated nerve fibers, and participates in a wide range of protein and fat metabolism. It is mainly used in clinical practice to treat pernicious anemia, and is also used in combination with folic acid to treat various megaloblastic anemias, anemia caused by antifolate drugs, and steatorrhea. It is also used to treat nervous system diseases such as neuritis, neural atrophy, etc., and is also used to treat liver diseases such as hepatitis and cirrhosis.

[0003] In recent years, the domestic and foreign markets have been demanding vitamin B 12 The demand for antibiotics is growing. According to statistics, the amount of wastewater produced by antibiotic production is more than 10 million tons, which has caused serious pollution to the environment. Therefore, eliminating the pollution caused by antibiotic wastewater to the environment is the most important prerequisite for achieving healthy and sustainable development of the antibiotic pharmaceutical industry. 12 The wastewater discharged during the production process mainly includes primary filtration waste liquid, refining waste liquid, exchange waste water, and cyanide-containing waste water. Among them, primary filtration waste liquid and refining waste liquid are high-concentration organic waste water, and exchange waste water and ground and equipment washing water are low-concentration organic waste water. High-concentration organic waste water is composed of primary filtration waste liquid and refining waste liquid, with a COD mass concentration of 60,000~70,000mg / L and a SO2 mass concentration of 3,000mg / L. The waste water is rich in organic acids, proteins, polysaccharides and other decomposition products, with complex components and great difficulty in treatment.

[0004] Vitamin B 12The pollutants in production wastewater are mainly organic matter, which is a natural substance with good biodegradability and high concentration, and belongs to high-concentration organic wastewater. The large amount of organic matter such as carbohydrates, fats, proteins, cellulose, etc. contained in high-concentration organic wastewater puts great pressure on the environment, which is itself a usable resource. Turning this resource into treasure can not only maintain a good ecological environment, but also improve economic benefits and promote green sustainable development. At present, the treatment methods of high-concentration organic wastewater mainly include physicochemical treatment and biological treatment. Physicochemical treatment is a method of converting pollutant components in wastewater into harmless substances by applying physical and chemical effects and their principles to purify wastewater, such as photochemical coagulation, oxidation-adsorption, incineration, extraction, wet catalytic oxidation, electrochemical and membrane separation. Biological treatment of wastewater is a method of using microorganisms to degrade pollutants in water as their own nutrition and energy, while purifying wastewater. Whether from the perspective of protecting and rationally utilizing water resources, or from the actual needs of enterprises to meet more stringent emission standards, it is of great practical significance to study the treatment and resource utilization of typical fermentation pharmaceutical production wastewater. Therefore, the present invention utilizes vitamin B 12 The waste liquid is used to prepare a liquid fertilizer with excellent absorption and long-lasting effect. Summary of the invention

[0005] The present invention aims to provide a vitamin B 12 The invention discloses a method for preparing liquid fertilizer from waste liquid, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: A B vitamin 12 The invention discloses a method for preparing liquid fertilizer from waste liquid. The liquid fertilizer is obtained by mixing protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water.

[0007] As an optimization, the slow-release phosphorus-nitrogen polymer is prepared by mixing urea, formaldehyde and dimethyl hydrogen phosphate.

[0008] As an optimization, the protease hydrolysate is obtained by flash-exploding solid protein and then hydrolyzing it with trypsin and subtilisin.

[0009] As an optimization, the regenerated mixed salt is obtained by acidifying the filtrate with sulfuric acid, adding potassium hydroxide and concentrating under reduced pressure.

[0010] As an optimization, the solid protein and filtrate are composed of vitamin B 12 The waste liquid is filtered, subjected to alkaline pretreatment and then separated.

[0011] As an optimization, the vitamin B 12 The waste liquid comes from Shijiazhuang Huarong Pharmaceutical Factory.

[0012] A B vitamin 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid is filtered through a 50-70 mesh nylon mesh, and calcium hydroxide is added to adjust the pH to 8-9. After stirring at 300-400 rpm until the volume of the flocs remains unchanged, the solid protein and filtrate are obtained. The filtrate is adjusted to a pH of 2-4 with sulfuric acid, stirred at 200-300 rpm for 20-40 min, and adjusted to a pH of 7-9 with potassium hydroxide, refluxed for 2-4 h, and concentrated under reduced pressure until the components are powdery, and dried at 50-60°C for 11-13 h to obtain a regenerated mixed salt. (2) Treat the solid protein in a steam flash explosion reactor at 3-5 MPa for 4-6 min, then release the pressure within 0.05-0.15 s, crush and sieve through 50-70 mesh to obtain protein powder; mix the protein powder, trypsin, subtilisin and urea solution in a mass ratio of 1:(0.12-0.13):(0.07-0.09):(14-16), add sodium hydroxide to adjust the solution pH to 8-9, perform enzymolysis at 55-65°C for 7-9 h, and then filter to obtain a protein hydrolyzate; (3) Mix urea, formaldehyde solution and deionized water in a mass ratio of 1:(2.6-2.8):(4-6), add 4%-6% potassium hydroxide solution to adjust the pH to 7-9, stir at 20-30°C and 100-200 rpm for 1-3 h, spin dry under reduced pressure in a water bath at 45-55°C, and dry at 35-45°C for 1-3 h, add deionized water 1.0-1.2 times the mass of urea, adjust the pH to 7-9 with potassium hydroxide solution, and place in a water bath for 5-15 min, add 1.4-1.5 times the mass of urea dimethyl hydrogen phosphate aqueous solution, heat to 75-85°C at 3-5°C / min, continue stirring for 35-45 min, dry at 95-105°C for 1-3 h, cool to 50-60°C, and dry to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:(0.1-0.3):(0.4-0.6):(0.4-0.6):(1.7-1.8), and adjust the pH value with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0013] As an optimization, the reflux temperature in step (1) is 90-100°C.

[0014] As an optimization, the mass fraction of the urea solution in step (2) is 1%~2%.

[0015] As an optimization, the mass fraction of the formaldehyde solution in step (3) is 36% to 38%.

[0016] As an optimization, the mass fraction of the potassium hydroxide solution in step (3) is 4% to 6%.

[0017] As an optimization, the water bath temperature in step (3) is 55-65°C.

[0018] As an optimization, the mass fraction of the dimethyl hydrogen phosphate aqueous solution in step (3) is 33% to 34%.

[0019] As an optimization, the reaction equation of the slow-release phosphorus-nitrogen polymer in step (3) is: .

[0020] As an optimization, the pH range adjusted by potassium hydroxide in step (4) is 5-6.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are: The present invention adds vitamin B 12 The waste liquid is filtered and then subjected to alkaline pretreatment to separate solid protein and filtrate; the filtrate is acidified with sulfuric acid, potassium hydroxide is added and concentrated under reduced pressure to obtain regenerated mixed salt; the solid protein is flash-exploded and then enzymatically hydrolyzed with trypsin and subtilisin to obtain a proteinase hydrolysate; urea, formaldehyde and dimethyl hydrogen phosphate are mixed to obtain a slow-release phosphorus-nitrogen polymer; the proteinase hydrolysate, the regenerated mixed salt, fulvic acid, the slow-release phosphorus-nitrogen polymer and deionized water are evenly mixed to obtain liquid fertilizer.

[0022] First, vitamin B 12 After the waste liquid is filtered, it is subjected to alkaline pretreatment to separate the solid protein and the filtrate; the filtrate is acidified with sulfuric acid, potassium hydroxide is added and concentrated under reduced pressure to obtain a regenerated mixed salt; the solid protein is subjected to flash explosion treatment, and then enzymatically hydrolyzed with trypsin and subtilisin to obtain a protease hydrolyzate; vitamin B is removed by alkali treatment 12 Waste liquid is separated into solid protein and filtrate; solid protein is treated by steam flash explosion technology and composite enzymatic hydrolysis technology. Steam explosion increases the solubility of nitrogen, improves the enzymatic hydrolysis effect of trypsin and subtilisin, and converts protein macromolecules into amino acid organic small molecules that can be directly absorbed by plant roots, promotes the rapid absorption of nitrogen sources by crops, and improves the nitrogen absorption rate of liquid fertilizer; Vitamin B 12It is produced by propionic acid bacteria fermentation. The waste liquid contains a large amount of ammonium propionate salt. It is acidified with non-volatile sulfuric acid to convert the ammonium propionate salt into free acid, and then concentrated by potassium hydroxide precipitation to obtain a regenerated mixed salt containing potassium sulfate and potassium propionate salt. Potassium propionate has a strong bactericidal or antibacterial effect on bacteria and molds, and can effectively extend the shelf life of liquid fertilizers and the anti-mildew properties of plants. Potassium sulfate is a large amount of element fertilizer required for plant growth, which can promote plant growth, increase crop yield and quality, and enhance crop resistance. At the same time, the use of sulfuric acid acidification and potassium hydroxide precipitation can efficiently utilize vitamin B 12 The elemental composition in the waste liquid can reduce the amount of waste liquid discharged, and the discharged waste liquid can be concentrated and dried and used as feed B 12 Filler, simple process, effectively improves vitamin B 12 Utilization rate of waste liquid.

[0023] Secondly, urea, formaldehyde and dimethyl hydrogen phosphate are mixed to obtain a slow-release phosphorus-nitrogen polymer; protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus-nitrogen polymer and deionized water are mixed to obtain liquid fertilizer; urea, diammonium sulfate and formaldehyde are polymerized into a slow-release phosphorus-nitrogen polymer under mild conditions to reduce the salinity coefficient of the soil after the fertilizer is applied, while controlling the rate of nutrient release, reducing nutrient loss, extending the action time of the fertilizer, and improving the long-term release of elements of the liquid fertilizer; fulvic acid is added to chelate phosphorus elements, minerals and nutrients in the soil and fertilizer, stabilize the effective ingredients, improve the nutrient mobility in the soil, promote the absorption and utilization of elements by plant roots, and extend the action time of the fertilizer. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] Embodiment 1: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12The waste liquid was filtered with a 50-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8. After stirring at 300 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 2 with sulfuric acid, stirred at 200 rpm for 30 min, and adjusted to pH 7 with potassium hydroxide. The filtrate was refluxed at 90° C. for 3 h, and concentrated under reduced pressure until the components therein were powdery, and dried at 50° C. for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 3 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 50 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1% urea solution were mixed in a mass ratio of 1:0.12:0.07:14, sodium hydroxide was added to adjust the solution pH to 8, and the solution was enzymatically hydrolyzed at 55°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 36% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.6:4, and a 4% potassium hydroxide solution was added to adjust the pH to 7. The mixture was stirred at 20°C and 100 rpm for 3 h, and the mixture was dried under reduced pressure in a 45°C water bath and dried at 35°C for 2 h. Deionized water in an amount 1.0 times the mass of the urea was added, and the pH was adjusted to 7 with a 4% potassium hydroxide solution. The mixture was in a 55°C water bath for 10 min, and a 33% dimethyl hydrogen phosphate aqueous solution in an amount 1.4 times the mass of the urea was added. The mixture was heated to 75°C at a rate of 3°C / min, and the mixture was stirred for 40 min. The mixture was dried at 95°C for 2 h, and the mixture was cooled to 50°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer. (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.1:0.4:0.4:1.7, and adjust the pH to 5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0026] Embodiment 2: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 70-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 9. After stirring at 400 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 4 with sulfuric acid, stirred at 300 rpm for 30 min, and adjusted to pH 9 with potassium hydroxide. The filtrate was refluxed at 100°C for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 60°C for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 5 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 70 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 2% urea solution were mixed in a mass ratio of 1:0.13:0.09:16, sodium hydroxide was added to adjust the solution pH to 9, and the solution was enzymolyzed at 65°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 38% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.8:6, and a 6% potassium hydroxide solution was added to adjust the pH to 9. The mixture was stirred at 30°C and 200 rpm for 2 h, and the mixture was dried under reduced pressure in a 55°C water bath and dried at 45°C for 2 h. Deionized water in an amount 1.2 times the mass of the urea was added, and the pH was adjusted to 9 with a 6% potassium hydroxide solution. The mixture was heated to 85°C at a rate of 5°C / min and stirred for 40 min. The mixture was dried at 105°C for 2 h, and the mixture was cooled to 60°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer. (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.3:0.6:0.6:1.8, and adjust the pH to 6 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0027] Embodiment 3: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 95°C for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 55°C for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 60°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 25°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 50°C water bath, and dried at 40°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 80°C at a rate of 4°C / min, stirring was continued for 40 min, the mixture was dried at 100°C for 2 h, the temperature was reduced to 55°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0028] Embodiment 4: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 90° C. for 3 h, and concentrated under reduced pressure until the components therein were powdery, and dried at 50° C. for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 55°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 20°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 45°C water bath, and dried at 35°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 75°C at a rate of 3°C / min, stirring was continued for 40 min, the mixture was dried at 95°C for 2 h, the temperature was lowered to 50°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0029] Embodiment 5: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 100° C. for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 60° C. for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 65°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 30°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 55°C water bath, and dried at 45°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 85°C at a rate of 5°C / min, stirring was continued for 40 min, the mixture was dried at 105°C for 2 h, the temperature was reduced to 60°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0030] Comparative Example 1: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 95°C for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 55°C for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 60°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Mix the protein hydrolysate, regeneration mixed salt, urea, dimethyl hydrogen phosphate, humic acid and deionized water in a mass ratio of 1:0.2:0.13:0.06:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0031] Comparative Example 2: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 95°C for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 55°C for 12 h to obtain a regenerated mixed salt. (2) Grinding the solid protein and sieving it through a 60-mesh screen to obtain protein powder; mixing the protein powder, trypsin, subtilisin and 1.5% urea solution in a mass ratio of 1:0.125:0.08:15, adding sodium hydroxide to adjust the pH of the solution to 8.5, performing enzymatic hydrolysis at 60°C for 8 hours and then filtering to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 25°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 50°C water bath, and dried at 40°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 80°C at a rate of 4°C / min, stirring was continued for 40 min, the mixture was dried at 100°C for 2 h, the temperature was reduced to 55°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0032] Comparative Example 3: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered with a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein and filtrate were obtained again. The filtrate was adjusted to pH 3 with sulfuric acid, stirred at 250 rpm for 30 min, and adjusted to pH 8 with potassium hydroxide. The filtrate was refluxed at 95°C for 3 h, and concentrated under reduced pressure until the components were powdery, and dried at 55°C for 12 h to obtain a regenerated mixed salt. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 60°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 25°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 50°C water bath, and dried at 40°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 80°C at a rate of 4°C / min, stirring was continued for 40 min, the mixture was dried at 100°C for 2 h, the temperature was reduced to 55°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0033] Comparative Example 4: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered through a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein was obtained after filtering again. (2) The solid protein was treated in a steam flash explosion reactor at 4 MPa for 5 min, then the pressure was released within 0.1 s, and the protein powder was crushed and sieved through 60 mesh to obtain protein powder; the protein powder, trypsin, subtilisin and 1.5% urea solution were mixed in a mass ratio of 1:0.125:0.08:15, sodium hydroxide was added to adjust the solution pH to 8.5, and the solution was enzymolyzed at 60°C for 8 h and then filtered to obtain a protease hydrolyzate; (3) Urea, 37% formaldehyde solution and deionized water were mixed in a mass ratio of 1:2.7:5, 5% potassium hydroxide solution was added to adjust the pH to 8, the mixture was stirred at 25°C and 150 rpm for 2 h, the mixture was dried under reduced pressure in a 50°C water bath, and dried at 40°C for 2 h, 1.1 times the mass of urea of ​​deionized water was added, the pH was adjusted to 8 with 5% potassium hydroxide solution, the mixture was heated to 80°C at a rate of 4°C / min, stirring was continued for 40 min, the mixture was dried at 100°C for 2 h, the temperature was reduced to 55°C and dried to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, filtrate, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:0.2:0.5:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

[0034] Comparative Example 5: A B vitamin 12 Method for preparing liquid fertilizer from waste liquid, the vitamin B 12 The method for preparing liquid fertilizer from waste liquid comprises the following preparation steps: (1) Vitamin B 12 The waste liquid was filtered through a 60-mesh nylon mesh, and calcium hydroxide was added to adjust the pH to 8.5. After stirring at 350 rpm until the volume of the flocs remained unchanged, the solid protein was obtained after filtering again. (2) Grinding the solid protein and sieving it through a 60-mesh screen to obtain protein powder; mixing the protein powder, trypsin, subtilisin and 1.5% urea solution in a mass ratio of 1:0.125:0.08:15, adding sodium hydroxide to adjust the pH of the solution to 8.5, performing enzymatic hydrolysis at 60°C for 8 hours and then filtering to obtain a protease hydrolyzate; (3) Mix the protein hydrolysate, filtrate, fulvic acid, urea, potassium dihydrogen phosphate and deionized water in a mass ratio of 1:0.2:0.13:0.06:0.5:1.75, and adjust the pH to 5.5 with potassium hydroxide in small amounts several times to obtain liquid fertilizer.

[0035] Test Case

[0036] 1. Long-term effect Test method: 1 mL of the liquid fertilizer obtained in each embodiment and the comparative example was respectively put into 150 mL of deionized water, and 2 mL of liquid sample was taken on the 30th day. The phosphorus concentration was determined at a wavelength of 700 nm using a molybdenum blue colorimeter method, and the phosphorus release rate was calculated as phosphorus release amount / phosphorus addition amount*100%.

[0037] 2. Proteinase hydrolysis rate Test method: The solid protein and protease hydrolysate obtained in each embodiment and comparative example were used to measure the total nitrogen content (N0) in the solid protein and the free amino acid content (N) in the protease hydrolysate, and the protein degradation rate was calculated as N / N0*100%.

[0038] 3. Waste liquid utilization rate Test method: The vitamin B used in each embodiment and comparative example 12 The wastewater volume (V0) and BOD load (BOD0) of the waste liquid were measured, and then the wastewater volume (V1) and BOD load (BOD1) in the waste liquid produced by each embodiment and the comparative example were measured, and the volume reduction rate [= (V0-V1) / V0*100%] and the BOD load reduction rate [= (V0-V1) / V0*100%] were calculated.

[0039] Table 1 below shows the data values ​​of the liquid fertilizers prepared using Examples 1 to 5 of the present invention.

[0040] Table 1

[0041] Table 2 below shows the analysis results of the long-term effectiveness, absorbability and waste liquid utilization rate of the liquid fertilizers prepared by Examples 1 to 5 of the present invention and Comparative Examples 1 to 5.

[0042] Table 2

[0043] From the comparison of the experimental data of Examples 1 to 5 and Comparative Examples 1 to 5 in Table 2, it can be found that the liquid fertilizer prepared by the present invention has good long-term effectiveness, easy absorption and waste liquid utilization rate.

[0044] By comparison, the phosphorus release rates of Examples 1, 2, 3, 4, and 5 are lower than those of Comparative Example 1, which indicates that urea, diammonium sulfate, and formaldehyde are polymerized into a slow-release phosphorus-nitrogen polymer under mild conditions, thereby reducing the salinity coefficient of the soil after fertilizer application, controlling the rate of nutrient release, reducing nutrient loss, extending the action time of the fertilizer, and improving the long-term release of elements of the liquid fertilizer.

[0045] By comparison, the protein hydrolysis rates of Examples 1, 2, 3, 4, and 5 are higher than those of Comparative Example 2, which illustrates that the steam flash explosion technology and the composite enzymatic hydrolysis technology are used to treat solid protein. Steam explosion increases the solubility of nitrogen, improves the enzymatic hydrolysis effect of trypsin and subtilisin, converts protein macromolecules into amino acid organic small molecules that can be directly absorbed by plant roots, promotes the rapid absorption of nitrogen sources by crops, and improves the nitrogen absorption rate of liquid fertilizers.

[0046] By comparison, the phosphorus release rates of Examples 1, 2, 3, 4, and 5 are lower than those of Comparative Example 3, indicating that the addition of fulvic acid chelates phosphorus elements, minerals, and nutrients in soil and fertilizers, stabilizes effective ingredients, improves nutrient mobility in the soil, promotes the absorption and utilization of elements by plant roots, and prolongs the action time of fertilizers. By comparison, the waste liquid discharge of Examples 1, 2, 3, 4, and 5 compared with Comparative Examples 1, 2, and 3 was reduced by more than 90%, and the BOD load was reduced by more than 80%, indicating that the use of sulfuric acid acidification and potassium hydroxide precipitation can efficiently utilize vitamin B 12 The elemental composition in the waste liquid can reduce the amount of waste liquid discharged, and the discharged waste liquid can be concentrated and dried and used as feed B 12 Filler, simple process, effectively improves vitamin B 12 Utilization rate of waste liquid.

[0047] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A B vitamin 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The liquid fertilizer is obtained by mixing protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water; The slow-release phosphorus-nitrogen polymer is prepared by mixing urea, formaldehyde and dimethyl hydrogen phosphate; The protease hydrolysate is obtained by flash-exploding solid protein and then hydrolyzing it with trypsin and subtilisin; The regenerated mixed salt is obtained by acidifying the filtrate with sulfuric acid, adding potassium hydroxide and concentrating under reduced pressure; The solid protein and the filtrate are vitamin B 12 The waste liquid is filtered, subjected to alkaline pretreatment and then separated.

2. A B vitamin 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The method comprises the following preparation steps: (1) Vitamin B 12 The waste liquid is filtered through a 50-70 mesh nylon mesh, and calcium hydroxide is added to adjust the pH to 8-9. After stirring at 300-400 rpm until the volume of the flocs remains unchanged, the solid protein and filtrate are obtained. The filtrate is adjusted to a pH of 2-4 with sulfuric acid, stirred at 200-300 rpm for 20-40 min, and adjusted to a pH of 7-9 with potassium hydroxide, refluxed for 2-4 h, and concentrated under reduced pressure until the components are powdery, and dried at 50-60°C for 11-13 h to obtain a regenerated mixed salt. (2) Treat the solid protein in a steam flash explosion reactor at 3-5 MPa for 4-6 min, then release the pressure within 0.05-0.15 s, crush and sieve through 50-70 mesh to obtain protein powder; mix the protein powder, trypsin, subtilisin and urea solution in a mass ratio of 1:(0.12-0.13):(0.07-0.09):(14-16), add sodium hydroxide to adjust the solution pH to 8-9, perform enzymolysis at 55-65°C for 7-9 h, and then filter to obtain a protein hydrolyzate; (3) Mix urea, formaldehyde solution and deionized water in a mass ratio of 1:(2.6-2.8):(4-6), add 4%-6% potassium hydroxide solution to adjust the pH to 7-9, stir at 20-30°C and 100-200 rpm for 1-3 h, spin dry under reduced pressure in a water bath at 45-55°C, and dry at 35-45°C for 1-3 h, add deionized water 1.0-1.2 times the mass of urea, adjust the pH to 7-9 with potassium hydroxide solution, keep in a water bath for 5-15 min, add 1.4-1.5 times the mass of urea dimethyl hydrogen phosphate aqueous solution, heat to 75-85°C at 3-5°C / min, continue stirring for 35-45 min, dry at 95-105°C for 1-3 h, cool to 50-60°C and dry to constant weight to obtain a slow-release phosphorus-nitrogen polymer; (4) Mix the protein hydrolysate, regeneration mixed salt, fulvic acid, slow-release phosphorus and nitrogen polymer and deionized water in a mass ratio of 1:(0.1-0.3):(0.4-0.6):(0.4-0.6):(1.7-1.8), and adjust the pH value with potassium hydroxide in small amounts multiple times to obtain liquid fertilizer.

3. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The reflux temperature in step (1) is 90-100°C.

4. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The mass fraction of the urea solution in step (2) is 1% to 2%.

5. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The mass fraction of the formaldehyde solution in step (3) is 36% to 38%.

6. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The mass fraction of the potassium hydroxide solution in step (3) is 4% to 6%.

7. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The water bath temperature in step (3) is 55-65°C.

8. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The mass fraction of the dimethyl hydrogen phosphate aqueous solution in step (3) is 33% to 34%.

9. A vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The reaction equation of the slow-release phosphorus-nitrogen polymer in step (3) is: 。 10. Vitamin B according to claim 2 12 The method for preparing liquid fertilizer from waste liquid is characterized in that: The pH range adjusted by potassium hydroxide in step (4) is 5-6.

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