Process for producing liquid fertilizer by utilizing tylosin waste liquid

Abstract

The invention discloses a process for producing a liquid fertilizer by utilizing tylosin waste liquid, and relates to the field of liquid fertilizers. When the tylosin waste liquid is used for producing the liquid fertilizer, corn straw and calcium carbonate are crushed and carbonized, then are grafted with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and are loaded with azomonas to obtain functional biochar; uniformly mixing biochar and monopotassium phosphate to prepare slow-release phosphorus biochar; digesting the seaweed meal, and precipitating to obtain a filter cake; carrying out alkali treatment on the tylosin waste liquid, and then treating the tylosin waste liquid and the filter cake by using a composite clastic enzyme to obtain a composite enzymatic hydrolysate; and mixing the composite enzymatic hydrolysate, the functionalized biochar, urea, the slow-release phosphorus biochar, potassium sulfate and deionized water to obtain the liquid fertilizer. The liquid fertilizer produced by utilizing the tylosin waste liquid has excellent nitrogen retention property, phosphorus slow release property and tylosin removal property.

Description

Technical Field

[0001] The invention relates to the field of liquid fertilizer, in particular to a process for producing liquid fertilizer by utilizing tylosin waste liquid. Background Art

[0002] Antibiotics are chemical substances that can have a significant impact on the growth or function of organisms through their own existence. Through bacterial culture, elements that threaten bacteria are found in this process. This is because of the existence of antibiotics, so antibiotics are discovered. With the progress of the times, more and more types of antibiotics have been discovered. Some of the main antibiotics are organisms extracted from raw materials, and the chemical structure of the manufacturing is improved to improve the efficacy of these antibiotics, saving many infected patients. The function of antibiotics is to inhibit the reproduction and growth of bacteria and viruses. In the environment of non-resistant strains, they will be killed by antibiotics, while the resistance of dominant bacteria will be caused by a large number of breeding. No matter how much antibiotics are contained in the ecological environment, it will have an impact on the environment. Antibiotic waste liquid can be recycled and reused in various ways, made into fertilizers, feed, etc., which can not only achieve the treatment and reuse of bacterial residues, but also create considerable economic benefits.

[0003] Veterinary antibiotics are mostly weak acid and weak alkaline compounds. Their lipophilicity allows them to pass through the cell membrane, thus avoiding losing their activity after exerting their therapeutic effects like other exogenous substances. They have good affinity with soil or sediment, so they can remain in the soil for a long time. These residual antibiotics may cause serious pollution to the soil environment and pose potential risks to the soil ecosystem and human health. The adsorption characteristics, photostability, bonding ability, degradation ability, leaching ability, physical and chemical properties, and microbial activity of veterinary antibiotics are the main reasons for the retention of veterinary antibiotics in soil and sediments. Generally, the physical and chemical properties of veterinary antibiotics determine their retention in solid media. Tetracycline, oxytetracycline, and sulfonamides are mostly weak acid and weak alkaline compounds with good affinity. They can combine with soil or sediment to form complexes, so they can remain in the soil for a relatively long time. According to current research, the degradation rates of tylosin, avermectin, quinol, etc. in soil are relatively high, while ivermectin, metronidazole, ceftriaxone, etc. are relatively average, and sarafloxacin is the most stable.

[0004] Tylosin, also known as tylosin and tylosin, is mostly an alkaline lipophilic compound with high inhibitory activity against Gram-positive bacteria and mycoplasma. It is a macrolide veterinary antibiotic produced by Streptomyces freundii. It has a white to light yellow powder structure, good solubility in water, high solubility in organic solvents, and is weakly alkaline. In order to promote the growth of animals, it is often used as an additive in feed. It can also be used for the prevention and control of infectious diseases such as mycoplasma, bacteria and Helicobacter in poultry. It has a strong inhibitory effect on a variety of Gram-positive bacteria, and also has a good inhibitory effect on some Gram-negative bacteria, Campylobacter (belonging to Vibrio) and spirochetes. It is fatally toxic to aquatic organisms (such as fish, shrimp, etc.).

[0005] Nitrogen is one of the essential nutrients for crop growth. The planting process often causes a large amount of nitrogen to enter the groundwater through leaching due to the production method of large amounts of water and fertilizer, thus causing environmental pollution. In the nitrogen cycle of the soil, there are mainly five processes, namely nitrogen fixation, ammoniation, assimilation, nitrification and denitrification. In agricultural production, improving nitrogen utilization efficiency, reducing nitrogen loss, and preventing nitrogen leaching during planting have become prominent issues that need to be urgently addressed to promote the green development of agriculture. Therefore, the present invention uses tylosin waste liquid to produce a liquid fertilizer with excellent nitrogen retention. Summary of the invention

[0006] The object of the present invention is to provide a process for producing liquid fertilizer by utilizing tylosin waste liquid, so as to solve the problems existing in the prior art.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: A process for producing liquid fertilizer by utilizing tylosin waste liquid. The liquid fertilizer is obtained by mixing composite enzymatic hydrolyzate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water.

[0008] As an optimization, the slow-release phosphorus biochar is prepared by mixing biochar and potassium dihydrogen phosphate; As an optimization, the composite enzymatic hydrolysate is obtained by treating the tylosin waste liquid with alkali and the filter cake with a composite decomposition enzyme.

[0009] As an optimization, the tylosin waste liquid comes from Zhejiang Hisun Pharmaceutical Co., Ltd.

[0010] As an optimization, the filter cake is obtained by digesting and precipitating seaweed powder.

[0011] As an optimization, the seaweed powder comes from Huamo (Shandong) Biotechnology Co., Ltd.

[0012] As an optimization, the functionalized biochar is obtained by crushing corn straw and calcium carbonate, carbonizing them, grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride, and then loading nitrogen monospermate.

[0013] As an optimization, the corn straw comes from Lingshou County Xinde Agricultural Products Co., Ltd.

[0014] A process for producing liquid fertilizer by using tylosin waste liquid comprises the following preparation steps: (1) Corn stalks and calcium carbonate were mixed in a mass ratio of 1:(0.2-0.3), crushed and sieved to 70-90 mesh, dried at 75-85°C for 11-13 h, placed in a tube furnace, and carbonized at a temperature of 5-15°C / min for 55-65 min in a nitrogen atmosphere to obtain biochar; biochar, sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:(0.7-0.8):(1-3):(9-11), stirred at 40-50°C and 100-200 rpm for 2-4 h, the pH of the solution was adjusted with glacial acetic acid, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 3-5 times respectively, dried at 55-65°C for 8-10 h, and sieved through a sieve to obtain modified biochar; (2) The modified biochar and LB liquid culture medium were mixed at a mass ratio of 1:(15-25), sterilized at 120-122°C for 15-25 min, inoculated with azomonas bacterial liquid, cultured at 27-29°C and 170-190 rpm / min for 23-25 ​​h, placed in a 10-20 μm sieve, and rinsed with deionized water for 1-2 min to obtain functionalized biochar; (3) Mix potassium dihydrogen phosphate and deionized water in a mass ratio of 1:(1000-2000), adjust the pH to 6-8 with 0.09-0.11 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution in a mass ratio of 1:(200-300), stir at 20-30°C and 100-200 r / min for 23-25 ​​h, filter with 0.4-0.5 μm filter paper, and dry at 55-65°C for 23-25 ​​h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and sodium carbonate solution in a mass ratio of 1:(15-25), digest at 55-65°C for 2-4 hours, and filter. Take the filtrate and adjust the pH to 1-2 with a 1%-3% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged, then filter. Dry at 60-70°C for 11-13 hours to obtain a filter cake. (5) Mix the tylosin waste liquid and sodium hydroxide in a mass ratio of 1:(0.02~0.03), let stand at 55~65℃ for 1~3h to obtain a treated liquid; mix the treated liquid, filter cake, composite decomposition enzyme and PBS buffer in a mass ratio of 1:(0.2~0.3):(0.06~0.07):(14~16), hydrolyze at 45~55℃ for 47~49h, then heat to 95~105℃ for inactivation for 9~11min, cool naturally to room temperature and centrifuge to obtain a composite enzymatic hydrolyzate; (6) Mix the composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water in a mass ratio of 1:(1-2):(0.4-0.6):(0.2-0.3):(0.2-0.3):(2-3) to obtain liquid fertilizer.

[0015] As an optimization, the carbonization temperature in step (1) is 450-550°C.

[0016] As an optimization, the mass fraction of the sodium hydroxide solution in step (1) is 1% to 3%.

[0017] As an optimization, the pH value adjusted by the glacial acetic acid in step (1) is 6-8.

[0018] As an optimization, the sieve specification in step (1) is 1 mm to 3 mm.

[0019] As an optimization, the concentration of the nitrogen monocytogenes solution in step (2) is: 0.9~1.1×10 7 .

[0020] As an optimization, the mass fraction of sodium carbonate in step (4) is 0.5%~1.5%.

[0021] As an optimization, the composite decomposing enzyme in step (5) is obtained by mixing cellulase, pectin hydrolase and protein hydrolase in a mass ratio of 2:1:1.

[0022] As an optimization, the pH of the PBS buffer in step (5) is 5-7.

[0023] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing liquid fertilizer produced by utilizing tylosin waste liquid, the present invention comprises the following steps: crushing and carbonizing corn stalks and calcium carbonate, grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride, and then loading nitrogen monospores to obtain functionalized biochar; mixing the biochar and potassium dihydrogen phosphate to obtain slow-release phosphorus biochar; digesting and precipitating seaweed powder to obtain a filter cake; then subjecting the tylosin waste liquid to an alkali treatment, and subjecting the filter cake to a composite decomposition enzyme treatment to obtain a composite enzymatic hydrolyzate; and mixing the composite enzymatic hydrolyzate, the functionalized biochar, urea, the slow-release phosphorus biochar, potassium sulfate and deionized water to obtain liquid fertilizer.

[0024] First, corn stalks and calcium carbonate were crushed and carbonized, then grafted with 3-chloro-2-hydroxypropyltrimethylammonium chloride and loaded with nitrogen-containing bacteria to obtain functionalized biochar. Biochar and potassium dihydrogen phosphate were mixed to obtain slow-release phosphorus biochar. After liquid fertilizer irrigation, a large amount of NH +4 -N is converted to NO -3 -N, using corn stalks and calcium carbonate crushed and carbonized and then grafted with 3-chloro-2-hydroxypropyltrimethylammonium chloride, it can adsorb NO in the soil through electrostatic attraction or ion exchange. -3 -N, and at the same time, biochar can provide more carbon sources for soil microorganisms, enable microorganisms to multiply in large numbers, promote the conversion of organic nitrogen to inorganic nitrogen, and reduce the leaching loss of organic nitrogen; by loading nitrogen-fixing nitrogen-monas, nitrogen gas is converted into ammonia, nitrogen is supplemented for the soil, and nitrogen utilization rate is improved; the biochar skeleton is oxidized by calcium carbonate, and the coordination formed with the oxidized carbon skeleton forms a good pore structure and rich metal active centers, and surface precipitation, ligand exchange and electrostatic attraction are used to assist chemical adsorption to efficiently enrich phosphate, so as to achieve the purpose of slow release of phosphorus, improve fertilizer utilization and reduce soil nutrient loss.

[0025] Secondly, the seaweed powder is digested and precipitated to obtain a filter cake; the tylosin waste liquid is then treated with alkali and then treated with a composite decomposition enzyme to obtain a composite enzymatic hydrolysate; the composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water are mixed to obtain a liquid fertilizer; the tylosin waste liquid is degraded and inactivated by sodium hydroxide to reduce the tylosin concentration in the waste liquid and avoid the generation of antibiotic residues and drug resistance; the residual protein in the tylosin waste liquid and the biological macromolecules in the seaweed powder are catalytically degraded by the composite decomposition enzyme to become small molecules that can be directly absorbed by crops, thereby supplementing the elements required for crop growth and promoting crop growth and development; urea, slow-release phosphorus biochar and potassium sulfate are added to further increase the supply of important nutrients. DETAILED DESCRIPTION

[0026] 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.

[0027] Embodiment 1: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 70 mesh, dried at 75 °C for 13 h, placed in a tube furnace, and heated to 450 °C at 5 °C / min in a nitrogen atmosphere for carbonization for 65 min to obtain biochar; the biochar, 1% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.7:1:9, stirred at 40 °C and 100 rpm for 4 h, the pH of the solution was adjusted to 6 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol three times respectively, dried at 55 °C for 10 h, and sieved through a 1 mm sieve to obtain modified biochar; (2) The modified biochar and LB liquid medium were mixed at a mass ratio of 1:15, sterilized at 120°C for 25 min, and inoculated with 0.9×10 7 The concentration of nitrogen mononas was cultured at 27 ° C and 170 rpm / min for 25 h, placed in a 10 μm sieve, and rinsed with deionized water for 1 min to obtain functionalized biochar; (3) Mix potassium dihydrogen phosphate and deionized water at a mass ratio of 1:1000, adjust the pH to 6 with 0.09 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution at a mass ratio of 1:200, stir at 20°C and 100 r / min for 25 h, filter with 0.4 μm filter paper, and dry at 55°C for 25 h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and 0.5% sodium carbonate solution in a mass ratio of 1:15, digest at 55°C for 4 h, and filter. Take the filtrate and adjust the pH to 1 with 1% phosphoric acid solution. Let it stand until the mass of the precipitate remains unchanged, then filter. Dry at 60°C for 13 h to obtain a filter cake. (5) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.02, and allowed to stand at 55°C for 3 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 5 were mixed at a mass ratio of 1:0.2:0.06:14, and enzymatically hydrolyzed at 45°C for 49 hours, then heated to 95°C for inactivation for 11 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (6) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1:0.4:0.2:0.2:2 to obtain liquid fertilizer.

[0028] Embodiment 2: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 80 mesh, dried at 80 °C for 12 h, placed in a tube furnace, heated to 500 °C at 10 °C / min in a nitrogen atmosphere, and carbonized for 60 min to obtain biochar; the biochar, 2% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.75:2:10, stirred at 45 °C and 150 rpm for 3 h, the pH of the solution was adjusted to 7 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 4 times respectively, dried at 60 °C for 9 h, and sieved through a 2 mm sieve to obtain modified biochar; (2) The modified biochar and LB liquid medium were mixed at a mass ratio of 1:20, sterilized at 121°C for 20 min, and inoculated with 1×10 7 The concentration of nitrogen mononas was cultured at 28 ° C and 180 rpm / min for 24 h, placed in a 15 μm sieve, and rinsed with deionized water for 1.5 min to obtain functionalized biochar; (3) Mix potassium dihydrogen phosphate and deionized water at a mass ratio of 1:1500, adjust the pH to 7 with 0.1 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution at a mass ratio of 1:250, stir at 25 °C and 150 r / min for 24 h, filter with 0.45 μm filter paper, and dry at 60 °C for 24 h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and 1% sodium carbonate solution in a mass ratio of 1:20, digest at 60°C for 3 h, and filter. Take the filtrate and adjust the pH to 1.5 with 2% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged and then filter. Dry at 65°C for 12 h to obtain a filter cake. (5) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.025, and allowed to stand at 60°C for 2 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6 were mixed at a mass ratio of 1:0.25:0.065:15, and enzymatically hydrolyzed at 50°C for 48 hours, then heated to 100°C for inactivation for 10 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (6) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1.5:0.5:0.25:0.25:2.5 to obtain liquid fertilizer.

[0029] Embodiment 3: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 85 mesh, dried at 83 °C for 11.5 h, placed in a tube furnace, heated to 525 °C at 12 °C / min in a nitrogen atmosphere, and carbonized for 57 min to obtain biochar; the biochar, 2.5% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.8:2.5:11, stirred at 47 °C and 175 rpm for 2.5 h, the pH of the solution was adjusted to 7.7 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 5 times respectively, dried at 63 °C for 8.5 h, and sieved through a 2.5 mm sieve to obtain modified biochar; (2) The modified biochar and LB liquid medium were mixed at a mass ratio of 1:22, sterilized at 122°C for 17 min, and inoculated with 1.1×10 7 The concentration of nitrogen mononas was cultured at 28.5 ° C and 185 rpm / min for 23.5 h, placed on a 17 μm sieve, and rinsed with deionized water for 2 min to obtain functionalized biochar; (3) Potassium dihydrogen phosphate and deionized water were mixed at a mass ratio of 1:1800, and the pH was adjusted to 7.5 with 0.11 mol / L sodium hydroxide solution to obtain a phosphate solution; biochar and phosphate solution were mixed at a mass ratio of 1:280, stirred at 28 °C and 170 r / min for 23.5 h, filtered with 0.5 μm filter paper, and dried at 65 °C for 23 h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and 1.3% sodium carbonate solution in a mass ratio of 1:25, digest at 65°C for 2 h, and filter. Take the filtrate and adjust the pH to 2 with 2.5% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged and then filter. Dry at 68°C for 11 h to obtain a filter cake. (5) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.03, and allowed to stand at 65°C for 1 hour to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6.5 were mixed at a mass ratio of 1:0.27:0.07:16, and enzymatically hydrolyzed at 55°C for 47 hours, then heated to 105°C for inactivation for 9 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (6) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1.7:0.6:0.3:0.3:3 to obtain liquid fertilizer.

[0030] Embodiment 4: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 90 mesh, dried at 85 °C for 11 h, placed in a tube furnace, heated to 550 °C at 15 °C / min in a nitrogen atmosphere, and carbonized for 55 min to obtain biochar; the biochar, 3% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.8:3:11, stirred at 50 °C and 200 rpm for 2 h, the pH of the solution was adjusted to 8 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 5 times respectively, dried at 65 °C for 8 h, and sieved through a 3 mm sieve to obtain modified biochar; (2) The modified biochar and LB liquid medium were mixed at a mass ratio of 1:25, sterilized at 122°C for 15 min, and inoculated with 1.1×10 7 The concentration of nitrogen mononas was cultured at 29 ° C and 190 rpm / min for 23 h, placed in a 20 μm sieve, and rinsed with deionized water for 2 min to obtain functionalized biochar; (3) Mix potassium dihydrogen phosphate and deionized water at a mass ratio of 1:2000, adjust the pH to 8 with 0.11 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution at a mass ratio of 1:300, stir at 30°C and 200 r / min for 23 h, filter with 0.5 μm filter paper, and dry at 65°C for 23 h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and 1.5% sodium carbonate solution in a mass ratio of 1:25, digest at 65°C for 2 h, and filter. Take the filtrate and adjust the pH to 2 with 3% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged and then filter. Dry at 70°C for 11 h to obtain a filter cake. (5) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.03, and allowed to stand at 65°C for 1 hour to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 7 were mixed at a mass ratio of 1:0.3:0.07:16, and enzymatically hydrolyzed at 55°C for 47 hours, then heated to 105°C for inactivation for 9 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (6) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:2:0.6:0.3:0.3:3 to obtain liquid fertilizer.

[0031] Comparative Example 1: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 80 mesh, dried at 80 °C for 12 h, placed in a tube furnace, heated to 500 °C at 10 °C / min in a nitrogen atmosphere, and carbonized for 60 min to obtain biochar; the biochar, 2% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.75:2:10, stirred at 45 °C and 150 rpm for 3 h, the pH of the solution was adjusted to 7 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 4 times respectively, dried at 60 °C for 9 h, and sieved through a 2 mm sieve to obtain modified biochar; (2) Mix seaweed powder and 1% sodium carbonate solution in a mass ratio of 1:20, digest at 60°C for 3 h, and filter. Take the filtrate and adjust the pH to 1.5 with 2% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged, then filter. Dry at 65°C for 12 h to obtain a filter cake. (3) Mix potassium dihydrogen phosphate and deionized water at a mass ratio of 1:1500, adjust the pH to 7 with 0.1 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution at a mass ratio of 1:250, stir at 25 °C and 150 r / min for 24 h, filter with 0.45 μm filter paper, and dry at 60 °C for 24 h to obtain slow-release phosphorus biochar; (4) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.025, and allowed to stand at 60°C for 2 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6 were mixed at a mass ratio of 1:0.25:0.065:15, and enzymatically hydrolyzed at 50°C for 48 hours, then heated to 100°C for inactivation for 10 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (5) The composite enzymatic hydrolysate, modified biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1.5:0.5:0.25:0.25:2.5 to obtain liquid fertilizer.

[0032] Comparative Example 2: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) Corn stalks were crushed and sieved to 80 mesh, dried at 80 °C for 12 h, placed in a tube furnace, and carbonized at 500 °C at a rate of 10 °C / min for 60 min in a nitrogen atmosphere to obtain biochar. Biochar and LB liquid culture medium were mixed at a mass ratio of 1:20, sterilized at 121 °C for 20 min, and inoculated with 1×10 7 The concentration of nitrogen mononas was cultured at 28 ° C and 180 rpm / min for 24 h, placed in a 15 μm sieve, and rinsed with deionized water for 1.5 min to obtain functionalized biochar; (2) Mix seaweed powder and 1% sodium carbonate solution in a mass ratio of 1:20, digest at 60°C for 3 h, and filter. Take the filtrate and adjust the pH to 1.5 with 2% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged, then filter. Dry at 65°C for 12 h to obtain a filter cake. (3) Mix potassium dihydrogen phosphate and deionized water at a mass ratio of 1:1500, adjust the pH to 7 with 0.1 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution at a mass ratio of 1:250, stir at 25 °C and 150 r / min for 24 h, filter with 0.45 μm filter paper, and dry at 60 °C for 24 h to obtain slow-release phosphorus biochar; (4) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.025, and allowed to stand at 60°C for 2 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6 were mixed at a mass ratio of 1:0.25:0.065:15, and enzymatically hydrolyzed at 50°C for 48 hours, then heated to 100°C for inactivation for 10 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (5) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1.5:0.5:0.25:0.25:2.5 to obtain liquid fertilizer.

[0033] Comparative Example 3: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 80 mesh, dried at 80 °C for 12 h, placed in a tube furnace, heated to 500 °C at 10 °C / min in a nitrogen atmosphere, and carbonized for 60 min to obtain biochar; the biochar, 2% sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:0.75:2:10, stirred at 45 °C and 150 rpm for 3 h, the pH of the solution was adjusted to 7 with glacial acetic acid and sodium hydroxide, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 4 times respectively, dried at 60 °C for 9 h, and sieved through a 2 mm sieve to obtain modified biochar; (2) The modified biochar and LB liquid medium were mixed at a mass ratio of 1:20, sterilized at 121°C for 20 min, and inoculated with 1×10 7 The concentration of nitrogen mononas was cultured at 28 ° C and 180 rpm / min for 24 h, placed in a 15 μm sieve, and rinsed with deionized water for 1.5 min to obtain functionalized biochar; (3) Mix seaweed powder and 1% sodium carbonate solution in a mass ratio of 1:20, digest at 60°C for 3 h, and filter. Take the filtrate and adjust the pH to 1.5 with 2% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged and then filter. Dry at 65°C for 12 h to obtain a filter cake. (4) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.025, and allowed to stand at 60°C for 2 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6 were mixed at a mass ratio of 1:0.25:0.065:15, and enzymatically hydrolyzed at 50°C for 48 hours, then heated to 100°C for inactivation for 10 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (5) The composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water were mixed in a mass ratio of 1:1.5:0.5:0.25:0.25:2.5 to obtain liquid fertilizer.

[0034] Comparative Example 4: A process for producing liquid fertilizer using tylosin waste liquid, the process for producing liquid fertilizer using tylosin waste liquid comprising the following steps: (1) The corn stalks were crushed and sieved to 80 mesh, dried at 80 °C for 12 h, placed in a tube furnace, and carbonized at 500 °C at a rate of 10 °C / min for 60 min in a nitrogen atmosphere to obtain biochar. (2) Mix seaweed powder and 1% sodium carbonate solution in a mass ratio of 1:20, digest at 60°C for 3 h, and filter. Take the filtrate and adjust the pH to 1.5 with 2% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged, then filter. Dry at 65°C for 12 h to obtain a filter cake. (3) The tylosin waste liquid and sodium hydroxide were mixed at a mass ratio of 1:0.025, and allowed to stand at 60°C for 2 hours to obtain a treated liquid; the treated liquid, filter cake, composite decomposition enzyme and PBS buffer with a pH of 6 were mixed at a mass ratio of 1:0.25:0.065:15, and enzymatically hydrolyzed at 50°C for 48 hours, then heated to 100°C for inactivation for 10 minutes, naturally cooled to room temperature, and centrifuged to obtain a composite enzymatic hydrolyzate; (4) Mix the composite enzymatic hydrolysate, biochar, urea, potassium dihydrogen phosphate, potassium sulfate and deionized water in a mass ratio of 1:1.5:0.5:0.25:0.25:2.5 to obtain liquid fertilizer.

[0035] Test Case 1. Nitrogen retention Test method: 300 mL of the liquid fertilizer obtained in each embodiment and the comparative example were respectively taken to irrigate 30 g of air-dried soil, left to stand for 3 days, and then irrigated the soil with 800 mL of deionized water. The nitrogen content in the effluent was tested with a UV-visible spectrometer, and the nitrogen loss rate was calculated as nitrogen content in the effluent / nitrogen content in the liquid fertilizer*100%.

[0036] 2. Tylosin residual rate Test method: The treated liquids obtained in each embodiment and comparative example were respectively measured for tylosin potency using a 1260 Infinity high performance liquid chromatograph, and the residual rate was calculated as follows: tylosin potency in the treated liquid / tylosin potency in the waste liquid*100%.

[0037] 3. Phosphorus sustained release 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 / total phosphorus content*100%.

[0038] Table 1 below shows the analysis results of nitrogen retention, phosphorus slow release and tylosin removal of liquid fertilizer produced using tylosin waste liquid using Examples 1 to 4 of the present invention and Comparative Examples 1 to 4.

[0039] Table 1

[0040] From the comparison of the experimental data of Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1, it can be found that the liquid fertilizer prepared by the present invention has good nitrogen retention, phosphorus slow release and tylosin removal properties.

[0041] By comparison, the nitrogen loss rates of Examples 1, 2, 3, and 4 are lower than those of Comparative Example 1, indicating that nitrogen gas is converted into ammonia by loading nitrogen-fixing Azotobacter, thereby supplementing nitrogen for the soil and improving nitrogen utilization.

[0042] By comparison, the nitrogen loss rates of Examples 1, 2, 3, and 4 are lower than those of Comparative Example 2, indicating that after liquid fertilizer irrigation, a large amount of NH +4 -N is converted to NO -3 -N, using corn stalks and calcium carbonate crushed and carbonized and then grafted with 3-chloro-2-hydroxypropyltrimethylammonium chloride, it can adsorb NO in the soil through electrostatic attraction or ion exchange. -3 -N, and at the same time, biochar can provide more carbon sources for soil microorganisms, allowing microorganisms to multiply in large numbers, promoting the conversion of organic nitrogen into inorganic nitrogen, and reducing the leaching loss of organic nitrogen.

[0043] By comparison, the phosphorus release rates of Examples 1, 2, 3, and 4 are lower than those of Comparative Example 3, which shows that the oxidation of the biochar skeleton by calcium carbonate forms a coordination bond with the oxidized carbon skeleton to form a good pore structure and rich metal active centers, and the surface precipitation, ligand exchange, and electrostatic attraction-assisted chemical adsorption efficiently enrich phosphates, thereby achieving the purpose of slow release of phosphorus, improving fertilizer utilization and reducing soil nutrient loss. By comparison, the residual rates of Examples 1, 2, 3, and 4 are similar to those of Comparative Examples 1, 2, 3, and 4, indicating that the tylosin waste liquid can be degraded and inactivated by using sodium hydroxide, thereby reducing the tylosin concentration in the waste liquid and avoiding the generation of antibiotic residues and drug resistance.

[0044] 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 process for producing liquid fertilizer using tylosin waste liquid, characterized in that: The liquid fertilizer is obtained by mixing composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water; The slow-release phosphorus biochar is prepared by mixing biochar and potassium dihydrogen phosphate; The composite enzymatic hydrolysate is obtained by treating tylosin waste liquid with alkali and filter cake with composite decomposition enzyme; The filter cake is obtained by digesting and precipitating the seaweed powder; The functionalized biochar is obtained by crushing corn stalks and calcium carbonate, carbonizing them, grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride, and then loading nitrogen monosperidinium.

2. A process for producing liquid fertilizer using tylosin waste liquid, characterized in that: The method comprises the following preparation steps: (1) Corn stalks and calcium carbonate were mixed in a mass ratio of 1:(0.2-0.3), crushed and sieved to 70-90 mesh, dried at 75-85°C for 11-13 h, placed in a tube furnace, and carbonized at a temperature of 5-15°C / min for 55-65 min in a nitrogen atmosphere to obtain biochar; biochar, sodium hydroxide solution, 3-chloro-2-hydroxypropyltrimethylammonium chloride and anhydrous ethanol were mixed in a mass ratio of 1:(0.7-0.8):(1-3):(9-11), stirred at 40-50°C and 100-200 rpm for 2-4 h, the pH of the solution was adjusted with glacial acetic acid, and the solution was allowed to stand until the mass of the precipitate remained unchanged, then filtered, washed with methanol and ethanol for 3-5 times respectively, dried at 55-65°C for 8-10 h, and sieved through a sieve to obtain modified biochar; (2) The modified biochar and LB liquid culture medium were mixed at a mass ratio of 1:(15-25), sterilized at 120-122°C for 15-25 min, inoculated with azomonas bacterial liquid, cultured at 27-29°C and 170-190 rpm / min for 23-25 ​​h, placed in a 10-20 μm sieve, and rinsed with deionized water for 1-2 min to obtain functionalized biochar; (3) Mix potassium dihydrogen phosphate and deionized water in a mass ratio of 1:(1000-2000), adjust the pH to 6-8 with 0.09-0.11 mol / L sodium hydroxide solution to obtain a phosphate solution; mix biochar and phosphate solution in a mass ratio of 1:(200-300), stir at 20-30°C and 100-200 r / min for 23-25 ​​h, filter with 0.4-0.5 μm filter paper, and dry at 55-65°C for 23-25 ​​h to obtain slow-release phosphorus biochar; (4) Mix seaweed powder and sodium carbonate solution in a mass ratio of 1:(15-25), digest at 55-65°C for 2-4 hours, and filter. Take the filtrate and adjust the pH to 1-2 with a 1%-3% phosphoric acid solution. Let it stand until the precipitate mass remains unchanged, then filter. Dry at 60-70°C for 11-13 hours to obtain a filter cake. (5) Mix the tylosin waste liquid and sodium hydroxide in a mass ratio of 1:(0.02~0.03), let stand at 55~65℃ for 1~3h to obtain a treated liquid; mix the treated liquid, filter cake, composite decomposition enzyme and PBS buffer in a mass ratio of 1:(0.2~0.3):(0.06~0.07):(14~16), hydrolyze at 45~55℃ for 47~49h, then heat to 95~105℃ for inactivation for 9~11min, cool naturally to room temperature and centrifuge to obtain a composite enzymatic hydrolyzate; (6) Mix the composite enzymatic hydrolysate, functionalized biochar, urea, slow-release phosphorus biochar, potassium sulfate and deionized water in a mass ratio of 1:(1-2):(0.4-0.6):(0.2-0.3):(0.2-0.3):(2-3) to obtain liquid fertilizer.

3. A process for producing liquid fertilizer by utilizing tylosin waste liquid according to claim 2, characterized in that, The carbonization temperature in step (1) is 450-550°C.

4. A process for producing liquid fertilizer by utilizing tylosin waste liquid according to claim 2, characterized in that, The mass fraction of the sodium hydroxide solution in step (1) is 1% to 3%.

5. A process for producing liquid fertilizer by utilizing tylosin waste liquid according to claim 2, characterized in that, The pH value adjusted by the glacial acetic acid in step (1) is 6-8.

6. A process for producing liquid fertilizer using tylosin waste liquid according to claim 2, characterized in that: The sieve size in step (1) is 1 mm to 3 mm.

7. A process for producing liquid fertilizer using tylosin waste liquid according to claim 2, characterized in that: The concentration of the azomonas bacterial solution in step (2) is: 0.9~1.1×10 7 .

8. A process for producing liquid fertilizer using tylosin waste liquid according to claim 2, characterized in that: The mass fraction of the sodium carbonate in step (4) is 0.5% to 1.5%.

9. A process for producing liquid fertilizer using tylosin waste liquid according to claim 2, characterized in that: The composite decomposing enzyme in step (5) is obtained by mixing cellulase, pectin hydrolase and protein hydrolase in a mass ratio of 2:1:

1.

10. A process for producing liquid fertilizer using tylosin waste liquid according to claim 2, characterized in that: The pH of the PBS buffer in step (5) is 5-7.

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