Process for preparing liquid fertilizer from acetylisovaleryltylosin tartrate waste liquid

Abstract

The invention discloses a process for preparing a liquid fertilizer from acetylisovaleryltylosin tartrate waste liquid, and relates to the field of fertilizers. When the liquid fertilizer is prepared from the acetylisovaleryltylosin tartrate waste liquid, graphene oxide, methyl alcohol and titanium dioxide are mixed, the mixture is mixed with the acetylisovaleryltylosin tartrate waste liquid through UV-B lamp illumination and dried, and the acetylisovaleryltylosin tartrate-loaded composite material is prepared; the preparation method comprises the following steps: mixing hollow mesoporous silica, deionized water and paenibacillus polymyxa, vacuumizing, returning to normal pressure, and repeating the operation to prepare modified hollow mesoporous silica; mixing the acetylisovaleryltylosin tartrate-loaded composite material with mineral oil, ethyl cellulose and modified hollow mesoporous silica in sequence, pouring the mixture into a membrane solution, and drying to obtain the sustained-release microcapsule; sargassum horneri is dried, ground, subjected to ultrasonic treatment, subjected to enzymolysis with cellulase and mixed with sustained-release microcapsules and oyster shell powder, and the liquid fertilizer is prepared. The liquid fertilizer prepared by the invention has good capabilities of slow release, photocatalytic degradation of acetylisovaleryltylosin tartrate, nitrogen fixation and soil pH regulation.

Description

Technical Field

[0001] The present invention relates to the field of fertilizers, and specifically to a process for preparing liquid fertilizer from tylvalosin waste liquid. Background Art

[0002] Seaweed is a marine organism with a wide global distribution and rich sources, and is widely used in many fields such as the food industry, industrial raw materials, agricultural and livestock production. Seaweed fertilizer is a new type of organic fertilizer that is natural, non-toxic and has no side effects. It contains rich minerals, polysaccharides and other bioactive substances, and has the effects of increasing crop yield and improving crop quality.

[0003] To make up for the decline in soil fertility caused by continuous sowing and increase crop yield, fertilizers are widely used in modern agriculture. However, due to reasons such as volatilization, loss, surface runoff and soil, the utilization efficiency of fertilizers by crops is very low, resulting in a large waste of manpower, material resources and financial resources. In addition, there are a large number of arid, semi-arid and desert areas in China. Therefore, in order to improve the nutrient utilization rate and increase food production, a process for preparing liquid fertilizer from tylvalosin waste liquid with water retention ability is introduced in this article. Summary of the Invention

[0004] The purpose of the present invention is to provide a process for preparing liquid fertilizer from tylvalosin waste liquid to solve the problems existing in the prior art.

[0005] A process for preparing liquid fertilizer from tylvalosin waste liquid, the process for preparing liquid fertilizer from tylvalosin waste liquid is obtained by drying, grinding, ultrasonicating, enzymolyzing with cellulase, and mixing with slow-release microcapsules and oyster shell powder of Sargassum horneri; The slow-release microcapsules are obtained by successively mixing the tylvalosin-loaded composite material with mineral oil, ethyl cellulose and modified hollow mesoporous silica, and then pouring it into the membrane solution and drying; The modified hollow mesoporous silica is obtained by mixing hollow mesoporous silica, deionized water and Paenibacillus polymyxa, evacuating, and then restoring to normal pressure, and repeating the operation; The membrane solution is obtained by mixing starch, low-polymerization-degree polyvinyl alcohol, sodium carboxymethyl cellulose, glycerol, ammonia water, polyethylene glycol, ethyl silicate, deionized water and a water repellent; The water repellent is obtained by reacting potassium hydroxide, stearic acid, triethanolamine and citric acid; The tylvalosin-loaded composite material is obtained by mixing tylvalosin waste liquid with graphene oxide-titanium dioxide composite material and drying; The graphene oxide-titanium dioxide composite material is obtained by mixing graphene oxide, methanol and titanium dioxide and irradiating with UV-B lamp light.

[0006] As an optimization, the process for preparing liquid fertilizer from tylosin waste liquid mainly includes the following preparation steps: (1) Take 4 - 6 parts by mass of deionized water, 0.2 - 0.25 parts of potassium hydroxide, 0.15 - 0.25 parts of stearic acid, 0.2 - 0.25 parts of triethanolamine, and 0.8 - 1 part of citric acid. Mix the deionized water and potassium hydroxide, heat to 65 - 75 °C, add stearic acid, cool to 45 - 55 °C, add triethanolamine, stir at 100 - 150 r / min for 10 - 20 min, let stand for 50 - 70 min, cool to 25 - 35 °C, add citric acid, let stand for 2 - 4 h, and adjust the pH to 6.5 - 7.5 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent. Take 1 - 2 parts by mass of starch, 0.7 - 0.9 parts of low - degree - of - polymerization polyvinyl alcohol, 0.07 - 0.09 parts of sodium carboxymethyl cellulose, 7 - 8 parts of glycerol, 0.8 - 1.2 parts of ammonia water, 0.15 - 0.25 parts of polyethylene glycol, 17 - 18 parts of deionized water, 1.8 - 2.2 parts of the water repellent, and 1.8 - 1.9 parts of ethyl silicate. Mix the starch, low - degree - of - polymerization polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 90 - 100 °C and 200 - 300 r / min for 50 - 70 min, add ammonia water and ethyl silicate, and continue to stir for 20 - 40 min to obtain a membrane solution. (2) Mix graphene oxide and titanium dioxide in a mass ratio of 1:3 - 5, grind to 130 - 170 mesh, add methanol 4 - 6 times the mass of graphene oxide, ultrasonicate for 100 - 140 min, under the conditions of 200 - 300 r / min, UV - B lamp, and nitrogen protection, irradiate with light for 6 - 8 h, and dry at room temperature for 22 - 24 h to obtain a graphene oxide - titanium dioxide composite material. Mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:8 - 12:2 - 3, ultrasonicate at 0 - 4 °C for 25 - 35 min, let stand under vacuum conditions for 25 - 30 min, restore to normal pressure, repeat the operation 2 - 4 times, centrifuge at 5000 r / min for 4 - 6 min, wash with ethanol 3 - 5 times, and vacuum - dry at - 10 - 0 °C for 11 - 13 h, grind to 30 - 50 mesh to obtain modified hollow mesoporous silica. Mix the tylosin waste liquid and the graphene oxide - titanium dioxide composite material in a mass ratio of 1:0.1 - 0.2, dry at 70 - 80 °C for 22 - 24 h to obtain a tylosin - loaded composite material. Mix the tylosin - loaded composite material and mineral oil in a mass ratio of 1:0.1 - 0.2, stir at 200 - 300 r / min for 3 - 5 min, then add ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil, continue to stir for 3 - 5 min, pour into the membrane solution, filter, and dry at - 10 - 0 °C for 22 - 26 h to obtain slow - release microcapsules. (3) Vacuum dry Sargassum horneri at 30 - 50 °C for 22 - 26 h, grind it to 60 - 100 mesh, ultrasonicate it at 60 - 70 °C and 400 - 500 W for 20 - 30 min, dry it at -10 - 0 °C for 22 - 26 h, add food-grade cellulase at 0.03 - 0.05 times the mass of Sargassum horneri and deionized water at 3 - 5 times the mass of Sargassum horneri, adjust the pH to 3.5 - 4.5 with 0.1 M hydrochloric acid solution, let it stand at 60 - 70 °C for 7 - 9 h, and then adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; wash oyster shells with deionized water 3 - 5 times and grind them to 80 - 100 mesh to obtain oyster shell powder; take 4 - 6 parts by mass of Sargassum horneri fertilizer, 2 - 3 parts by mass of oyster shell powder, and 1 - 1.4 parts by mass of slow-release microcapsules, and mix the Sargassum horneri fertilizer, oyster shell powder and slow-release microcapsules to obtain liquid fertilizer.

[0007] As an optimization, the ammonia water described in step (1) is industrial-grade ammonia water.

[0008] As an optimization, the starch described in step (1) is industrial-grade pregelatinized starch.

[0009] As an optimization, the degree of polymerization of the polyethylene glycol described in step (1) is 1000 - 1400.

[0010] As an optimization, the manufacturer from which the polyvinyl alcohol is purchased in step (1) is Dongguan Baojia Plastic Co., Ltd.

[0011] As an optimization, the sodium carboxymethyl cellulose described in step (1) is food-grade sodium carboxymethyl cellulose.

[0012] As an optimization, the glycerol described in step (1) is industrial-grade glycerol.

[0013] As an optimization, the hollow mesoporous silica described in step (2) is hollow mesoporous silica with a purity greater than 99.9%.

[0014] As an optimization, the Paenibacillus polymyxa described in step (2) is a water-soluble Paenibacillus polymyxa.

[0015] As an optimization, the mineral oil described in step (2) is industrial white mineral oil.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing liquid fertilizer from tilmicosin waste liquid, graphene oxide, methanol and titanium dioxide are mixed, irradiated with UV-B lamp and mixed with tilmicosin waste liquid, and then dried to obtain tilmicosin-loaded composite material; hollow mesoporous silica, deionized water and Paenibacillus polymyxa are mixed, evacuated and then returned to normal pressure, and the operation is repeated to obtain modified hollow mesoporous silica; the tilmicosin-loaded composite material is successively mixed with mineral oil, ethyl cellulose and modified hollow mesoporous silica, and then poured into the membrane liquid and dried to obtain sustained-release microcapsules; Sargassum horneri is dried, ground, ultrasonically treated, enzymatically hydrolyzed with cellulase, and mixed with the sustained-release microcapsules and oyster shell powder to obtain liquid fertilizer.

[0017] First, graphene oxide, methanol and titanium dioxide are mixed, irradiated with UV-B lamp and mixed with tilmicosin waste liquid, and then dried to obtain tilmicosin-loaded composite material; hollow mesoporous silica, deionized water and Paenibacillus polymyxa are mixed, evacuated and then returned to normal pressure, and the operation is repeated to obtain modified hollow mesoporous silica; graphene oxide, methanol and titanium dioxide are mixed, irradiated with UV-B lamp, and an inorganic composite material capable of photocatalytic degradation of tilmicosin can be obtained. Tilmicosin is loaded on its surface, which can not only degrade tilmicosin to avoid environmental pollution caused by antibiotics, but also convert tilmicosin into fertilizer that can be absorbed by plants; Paenibacillus polymyxa is loaded inside the hollow mesoporous silica. As a nitrogen-fixing bacterium, Paenibacillus polymyxa can achieve the effect of nitrogen fixation.

[0018] Second, the tilmicosin-loaded composite material is successively mixed with mineral oil, ethyl cellulose and modified hollow mesoporous silica, and then poured into the membrane liquid and dried to obtain sustained-release microcapsules; Sargassum horneri is dried, ground, ultrasonically treated, enzymatically hydrolyzed with cellulase, and mixed with the sustained-release microcapsules and oyster shell powder to obtain liquid fertilizer; then, a film is coated on the outside of the tilmicosin-loaded composite material and modified hollow mesoporous silica, and the nutrients in the decomposed tilmicosin can be slowly released; Sargassum horneri is enzymatically hydrolyzed under acidic conditions, and then oyster shell powder is added to adjust the pH of the fertilizer and improve the pH of acidic soil. Specific embodiments

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0020] Example 1 A process for preparing liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (1)Take 4 parts of deionized water, 0.2 parts of potassium hydroxide, 0.15 parts of stearic acid, 0.2 parts of triethanolamine, and 0.8 parts of citric acid by mass fraction. Mix the deionized water and potassium hydroxide, heat to 65 °C, add stearic acid, cool to 45 °C, add triethanolamine, stir at 100 r / min for 10 min, let stand for 50 min, cool to 25 °C, add citric acid, let stand for 2 h, and adjust the pH to 6.5 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; Take 1 part of starch, 0.7 parts of low-polymerization-degree polyvinyl alcohol, 0.07 parts of sodium carboxymethyl cellulose, 7 parts of glycerol, 0.8 parts of ammonia water, 0.15 parts of polyethylene glycol with a polymerization degree of 1000, 17 parts of deionized water, 1.8 parts of water repellent, and 1.8 parts of ethyl silicate by mass fraction. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 90 °C and 200 r / min for 50 min, add ammonia water and ethyl silicate, and continue to stir for 20 min to obtain a film solution; (2)Mix graphene oxide and titanium dioxide in a mass ratio of 1:3, grind to 130 mesh, add methanol 4 times the mass of graphene oxide, ultrasonicate for 100 min, irradiate with light for 6 h at 200 r / min, under a UV-B lamp, and under nitrogen protection, and dry at room temperature for 22 h to obtain a graphene oxide-titanium dioxide composite; Mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:8:2, ultrasonicate at 0 °C for 25 min, let stand under vacuum conditions for 25 min, restore to normal pressure, repeat the operation 2 times, centrifuge at 5000 r / min for 4 min, wash 3 times with ethanol, and vacuum dry at -10 °C for 11 h, grind to 30 mesh to obtain modified hollow mesoporous silica; Mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite in a mass ratio of 1:0.1, dry at 70 °C for 22 h to obtain a tilmicosin-loaded composite; Mix the tilmicosin-loaded composite and mineral oil in a mass ratio of 1:0.1, stir at 200 r / min for 3 min, then add ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil, continue to stir for 3 min, pour into the film solution, filter, and dry at -10 °C for 22 h to obtain slow-release microcapsules; (3)Vacuum dry Sargassum horneri at 30 °C for 22 h, grind to 60 mesh, ultrasonicate at 60 °C and 400 W for 20 min, dry at -10 °C for 22 h, add 0.03 times the mass of food-grade cellulase based on the mass of Sargassum horneri and 3 times the mass of deionized water based on the mass of Sargassum horneri, adjust the pH to 3.5 with 0.1 M hydrochloric acid solution, let stand at 60 °C for 7 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; Wash oyster shells 3 times with deionized water and grind to 80 mesh to obtain oyster shell powder; Take 4 parts of Sargassum horneri fertilizer, 2 parts of oyster shell powder, and 1 part of slow-release microcapsules by mass fraction, mix the Sargassum horneri fertilizer, oyster shell powder, and slow-release microcapsules to obtain a liquid fertilizer.

[0021] Example 2 A process for preparing liquid fertilizer from tylvalosin waste liquid mainly includes the following preparation steps: (1) Take 5 parts of deionized water, 0.225 parts of potassium hydroxide, 0.2 parts of stearic acid, 0.225 parts of triethanolamine, and 0.9 parts of citric acid by mass. Mix the deionized water and potassium hydroxide, heat to 75°C, add stearic acid, cool to 55°C, add triethanolamine, stir at 125 r / min for 10 min, let stand for 50 min, cool to 35°C, add citric acid, let stand for 2 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent. Take 1.5 parts of starch, 0.8 parts of low-polymerization-degree polyvinyl alcohol, 0.08 parts of sodium carboxymethyl cellulose, 7.5 parts of glycerol, 1 part of ammonia water, 0.2 parts of polyethylene glycol with a polymerization degree of 1200, 17.5 parts of deionized water, 2 parts of water repellent, and 1.85 parts of ethyl silicate by mass. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 100°C and 250 r / min for 50 min, add ammonia water and ethyl silicate, and continue to stir for 20 min to obtain a film solution; (2) Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind to 150 mesh, add methanol 5 times the mass of graphene oxide, sonicate for 100 min, irradiate with light for 6 h at 250 r / min under a UV-B lamp and nitrogen protection, and dry at room temperature for 22 h to obtain a graphene oxide-titanium dioxide composite material. Mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, sonicate at 4°C for 25 min, let stand under vacuum for 25 min, restore to normal pressure, repeat the operation 3 times, centrifuge at 5000 r / min for 4 min, wash 4 times with ethanol, vacuum dry at 0°C for 11 h, and grind to 40 mesh to obtain modified hollow mesoporous silica. Mix the tylvalosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 80°C for 22 h to obtain a tylvalosin-loaded composite material. Mix the tylvalosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 4 min, then add ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil, continue to stir for 3 min, pour into the film solution, filter, and dry at 0°C for 22 h to obtain a sustained-release microcapsule; (3) Vacuum dry Sargassum horneri at 850 °C for 228 h, grind it to 80 mesh, ultrasonicate it at 70 °C and 450 W for 20 min, dry it at 80 °C for 22 h, add food-grade cellulase at 0.04 times the mass of Sargassum horneri and deionized water at 4 times the mass of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, let it stand at 70 °C for 7 h, and then adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; wash oyster shells 4 times with deionized water and grind them to 90 mesh to obtain oyster shell powder; take 5 parts by mass of Sargassum horneri fertilizer, 2.5 parts by mass of oyster shell powder, and 1.2 parts by mass of slow-release microcapsules, and mix the Sargassum horneri fertilizer, oyster shell powder, and slow-release microcapsules to obtain liquid fertilizer.

[0022] Example 3 A process for preparing liquid fertilizer from tylosin waste liquid mainly includes the following preparation steps: (1) Take 5 parts by mass of deionized water, 0.225 parts by mass of potassium hydroxide, 0.2 parts by mass of stearic acid, 0.225 parts by mass of triethanolamine, and 0.9 parts by mass of citric acid. Mix deionized water and potassium hydroxide, heat to 70 °C, add stearic acid, cool to 50 °C, add triethanolamine, stir at 125 r / min for 15 min, let it stand for 60 min, cool to 30 °C, add citric acid, let it stand for 3 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; take 1.5 parts by mass of starch, 0.8 parts by mass of low-polymerization-degree polyvinyl alcohol, 0.08 parts by mass of sodium carboxymethyl cellulose, 7.5 parts by mass of glycerol, 1 part by mass of ammonia water, 0.2 parts by mass of polyethylene glycol with a polymerization degree of 1200, 17.5 parts by mass of deionized water, 2 parts by mass of water repellent, and 1.85 parts by mass of ethyl silicate. Mix starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 95 °C and 250 r / min for 60 min, add ammonia water and ethyl silicate, and continue to stir for 30 min to obtain a film solution. (2)Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind to 150 mesh, add methanol 5 times the mass of graphene oxide, sonicate for 120 min, under 250 r / min, UV-B lamp, and nitrogen protection, irradiate with light for 7 h, and dry at room temperature for 23 h to obtain a graphene oxide-titanium dioxide composite material; Mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, sonicate at 2°C for 30 min, stand still under vacuum conditions for 27.5 min, restore to normal pressure, repeat the operation 3 times, centrifuge at 5000 r / min for 5 min, wash 4 times with ethanol, and vacuum dry at -5°C for 12 h, grind to 40 mesh to obtain modified hollow mesoporous silica; Mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 75°C for 23 h to obtain a tilmicosin-loaded composite material; Mix the tilmicosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 4 min, then add ethyl cellulose equal in mass to the mineral oil and modified hollow mesoporous silica equal in mass to the mineral oil, continue to stir for 4 min, pour into the membrane solution, filter, and dry at -5°C for 24 h to obtain a sustained-release microcapsule; (3)Vacuum dry Sargassum horneri at 40°C for 24 h, grind to 80 mesh, sonicate at 65°C and 450 W for 25 min, dry at -5°C for 24 h, add food-grade cellulase 0.04 times the mass of Sargassum horneri and deionized water 4 times the mass of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, stand still at 65°C for 8 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; Wash oyster shells 4 times with deionized water and grind to 90 mesh to obtain oyster shell powder; Take 5 parts of Sargassum horneri fertilizer, 2.5 parts of oyster shell powder, and 1.2 parts of sustained-release microcapsule by mass, and mix the Sargassum horneri fertilizer, oyster shell powder, and sustained-release microcapsule to obtain a liquid fertilizer.

[0023] Example 4 A process for preparing liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (1)Take 5 parts of deionized water, 0.225 parts of potassium hydroxide, 0.2 parts of stearic acid, 0.225 parts of triethanolamine, and 0.9 parts of citric acid by mass fraction. Mix the deionized water and potassium hydroxide, heat to 65 °C, add stearic acid, cool to 45 °C, add triethanolamine, stir at 125 r / min for 20 min, let stand for 70 min, cool to 25 °C, add citric acid, let stand for 4 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; Take 1.5 parts of starch, 0.8 parts of low-polymerization-degree polyvinyl alcohol, 0.08 parts of sodium carboxymethyl cellulose, 7.5 parts of glycerol, 1 part of ammonia water, 0.2 parts of polyethylene glycol with a polymerization degree of 1200, 17.5 parts of deionized water, and 2 parts of water repellent, 1.85 parts of ethyl silicate by mass fraction. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose and deionized water, stir at 90 °C and 250 r / min for 70 min, add ammonia water and ethyl silicate, and continue to stir for 40 min to obtain a membrane liquid; (2)Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind to 150 mesh, add methanol 5 times the mass of graphene oxide, ultrasonicate for 140 min, under 250 r / min, UV-B lamp, and nitrogen protection, irradiate with light for 8 h, and dry at room temperature for 24 h to obtain a graphene oxide-titanium dioxide composite material; Mix hollow mesoporous silica, deionized water and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, ultrasonicate at 0 °C for 35 min, let stand under vacuum conditions for 30 min, restore to normal pressure, repeat the operation 3 times, centrifuge at 5000 r / min for 6 min, wash 4 times with ethanol, and vacuum dry at -10 °C for 13 h, grind to 40 mesh to obtain modified hollow mesoporous silica; Mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 70 °C for 24 h to obtain a tilmicosin-loaded composite material; Mix the tilmicosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 5 min, then add ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil, continue to stir for 5 min, pour into the membrane liquid, filter, and dry at -1 °C for 26 h to obtain a sustained-release microcapsule; (3)Sargassum horneri was vacuum dried at 30 °C for 26 h, ground to 80 mesh, sonicated at 60 °C and 450 W for 30 min, dried at -10 °C for 26 h, food-grade cellulase at 0.04 times the mass of Sargassum horneri and deionized water at 4 times the mass of Sargassum horneri were added, the pH was adjusted to 4 with 0.1 M hydrochloric acid solution, left standing at 60 °C for 9 h, and the pH was adjusted to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; The oyster shells were washed 4 times with deionized water and ground to 90 mesh to obtain oyster shell powder; 5 parts of Sargassum horneri fertilizer, 2.5 parts of oyster shell powder, and 1.2 parts of slow-release microcapsules were taken by mass fraction, and the Sargassum horneri fertilizer, oyster shell powder, and slow-release microcapsules were mixed to obtain liquid fertilizer.

[0024] Example 5 A process for preparing liquid fertilizer from tylosin waste liquid mainly includes the following preparation steps: (1)6 parts of deionized water, 0.25 part of potassium hydroxide, 0.25 part of stearic acid, 0.25 part of triethanolamine, and 1 part of citric acid were taken by mass fraction. The deionized water and potassium hydroxide were mixed, heated to 75 °C, stearic acid was added, cooled to 55 °C, triethanolamine was added, stirred at 150 r / min for 20 min, left standing for 70 min, cooled to 35 °C, citric acid was added, left standing for 4 h, and the pH was adjusted to 7.5 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; 2 parts of starch, 0.9 part of low-polymerization-degree polyvinyl alcohol, 0.09 part of sodium carboxymethyl cellulose, 8 parts of glycerol, 1.2 parts of ammonia water, 0.25 part of polyethylene glycol with a polymerization degree of 1400, 18 parts of deionized water, 2.2 parts of water repellent, and 1.9 parts of ethyl silicate were taken by mass fraction. The starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water were mixed, stirred at 100 °C and 300 r / min for 70 min, ammonia water and ethyl silicate were added, and stirring was continued for 40 min to obtain a membrane solution; (2)Graphene oxide and titanium dioxide were mixed at a mass ratio of 1:5, ground to 170 mesh, 6 times the mass of graphene oxide of methanol was added, ultrasonicated for 140 min, under 300 r / min, UV-B lamp, nitrogen protection, irradiated with light for 8 h, and dried at room temperature for 24 h to obtain a graphene oxide-titanium dioxide composite material; hollow mesoporous silica, deionized water and Paenibacillus polymyxa were mixed at a mass ratio of 1:12:3, ultrasonicated at 4 °C for 35 min, left standing for 30 min under vacuum conditions, restored to normal pressure, and the operation was repeated 4 times, centrifuged at 5000 r / min for 6 min, washed 5 times with ethanol, vacuum dried at 0 °C for 13 h, and ground to 50 mesh to obtain modified hollow mesoporous silica; the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material were mixed at a mass ratio of 1:0.2, dried at 80 °C for 24 h to obtain a tilmicosin-loaded composite material; the tilmicosin-loaded composite material and mineral oil were mixed at a mass ratio of 1:0.2, stirred at 300 r / min for 5 min, then ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil were added, and stirred for another 5 min, poured into the membrane solution, filtered, and dried at 0 °C for 26 h to obtain a sustained-release microcapsule; (3)Sargassum horneri was vacuum dried at 50 °C for 26 h, ground to 100 mesh, ultrasonicated at 70 °C and 500 W for 30 min, dried at 0 °C for 26 h, 0.05 times the mass of food-grade cellulase based on the mass of Sargassum horneri and 5 times the mass of deionized water based on the mass of Sargassum horneri were added, the pH was adjusted to 4.5 with 0.1 M hydrochloric acid solution, left standing at 70 °C for 9 h, and the pH was adjusted to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; the oyster shell was washed 5 times with deionized water and ground to 100 mesh to obtain oyster shell powder; 6 parts by mass of Sargassum horneri fertilizer, 3 parts by mass of oyster shell powder, and 1.4 parts by mass of the sustained-release microcapsule were taken, and the Sargassum horneri fertilizer, oyster shell powder and the sustained-release microcapsule were mixed to obtain a liquid fertilizer.

[0025] Comparative Example 1 A process for preparing a liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (1) Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind them to 150 mesh, add methanol five times the mass of graphene oxide, sonicate for 120 min, irradiate with light for 7 h at 250 r / min under a UV-B lamp and nitrogen protection, and dry at room temperature for 23 h to obtain a graphene oxide-titanium dioxide composite material; mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, sonicate at 2 °C for 30 min, let it stand for 27.5 min under vacuum conditions, restore to normal pressure, repeat the operation three times, centrifuge at 5000 r / min for 5 min, wash with ethanol four times, dry under vacuum at -5 °C for 12 h, and grind to 40 mesh to obtain modified hollow mesoporous silica; mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 75 °C for 23 h to obtain a tilmicosin-loaded composite material; mix the tilmicosin-loaded composite material and the modified hollow mesoporous silica in a mass ratio of 1:0.15 to obtain a sustained-release microcapsule; (2) Vacuum-dry Sargassum horneri at 40 °C for 24 h, grind it to 80 mesh, sonicate at 65 °C and 450 W for 25 min, dry at -5 °C for 24 h, add food-grade cellulase 0.04 times the mass of Sargassum horneri and deionized water four times the mass of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, let it stand at 65 °C for 8 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; wash oyster shells four times with deionized water and grind them to 90 mesh to obtain oyster shell powder; take 5 parts by mass of Sargassum horneri fertilizer, 2.5 parts by mass of oyster shell powder, 1 part by mass of the tilmicosin-loaded composite material, and 0.15 parts by mass of the modified hollow mesoporous silica, and mix the Sargassum horneri fertilizer, oyster shell powder, tilmicosin-loaded composite material, and modified hollow mesoporous silica to obtain a liquid fertilizer.

[0026] Test Example 2 A process for preparing a liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (4)Take 5 parts of deionized water, 0.225 parts of potassium hydroxide, 0.2 parts of stearic acid, 0.225 parts of triethanolamine, and 0.9 parts of citric acid by mass. Mix the deionized water and potassium hydroxide, heat to 70 °C, add stearic acid, cool to 50 °C, add triethanolamine, stir at 125 r / min for 15 min, let stand for 60 min, cool to 30 °C, add citric acid, let stand for 3 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent. Take 1.5 parts of starch, 0.8 parts of low-polymerization-degree polyvinyl alcohol, 0.08 parts of sodium carboxymethyl cellulose, 7.5 parts of glycerol, 1 part of ammonia water, 0.2 parts of polyethylene glycol with a polymerization degree of 1200, 17.5 parts of deionized water, and 2 parts of water repellent, 1.85 parts of ethyl silicate by mass. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 95 °C and 250 r / min for 60 min, add ammonia water and ethyl silicate, and continue to stir for 30 min to obtain a film solution; (5)Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind to 150 mesh, add methanol 5 times the mass of graphene oxide, ultrasonicate for 120 min, irradiate with light for 7 h at 250 r / min under a UV-B lamp and nitrogen protection, and dry at room temperature for 23 h to obtain a graphene oxide-titanium dioxide composite material. Mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 75 °C for 23 h to obtain a tilmicosin-loaded composite material. Mix the tilmicosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 4 min, then add ethyl cellulose with the same mass as the mineral oil, continue to stir for 4 min, pour into the film solution, filter, and dry at -5 °C for 24 h to obtain a sustained-release microcapsule; (6)Vacuum-dry Sargassum horneri at 40 °C for 24 h, grind to 80 mesh, ultrasonicate at 65 °C and 450 W for 25 min, dry at -5 °C for 24 h, add food-grade cellulase 0.04 times the mass of Sargassum horneri and deionized water 4 times the mass of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, let stand at 65 °C for 8 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer. Wash oyster shells 4 times with deionized water and grind to 90 mesh to obtain oyster shell powder. Take 5 parts of Sargassum horneri fertilizer, 2.5 parts of oyster shell powder, and 1.2 parts of sustained-release microcapsule by mass. Mix the Sargassum horneri fertilizer, oyster shell powder, and sustained-release microcapsule to obtain a liquid fertilizer.

[0027] Test Example 3 A process for preparing liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (1) Take 5 parts of deionized water, 0.225 parts of potassium hydroxide, 0.2 parts of stearic acid, 0.225 parts of triethanolamine, and 0.9 parts of citric acid by mass fraction. Mix the deionized water and potassium hydroxide, heat to 70 °C, add stearic acid, cool to 50 °C, add triethanolamine, stir at 125 r / min for 15 min, let stand for 60 min, cool to 30 °C, add citric acid, let stand for 3 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; Take 1.5 parts of starch, 0.8 parts of low-polymerization-degree polyvinyl alcohol, 0.08 parts of sodium carboxymethyl cellulose, 7.5 parts of glycerol, 1 part of ammonia water, 0.2 parts of polyethylene glycol with a polymerization degree of 1200, 17.5 parts of deionized water, and 2 parts of water repellent, 1.85 parts of ethyl silicate by mass fraction. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 95 °C and 250 r / min for 60 min, add ammonia water and ethyl silicate, and continue to stir for 30 min to obtain a film solution; (2) Mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, ultrasonicate at 2 °C for 30 min, let stand under vacuum conditions for 27.5 min, restore to normal pressure, repeat the operation 3 times, centrifuge at 5000 r / min for 5 min, wash 4 times with ethanol, vacuum dry at -5 °C for 12 h, and grind to 40 mesh to obtain modified hollow mesoporous silica; Mix the tilmicosin waste liquid and the modified hollow mesoporous silica in a mass ratio of 1:0.15, dry at 75 °C for 23 h to obtain a tilmicosin-loaded composite material; Mix the tilmicosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 4 min, then add an equal mass of ethyl cellulose of mineral oil, continue to stir for 4 min, pour into the film solution, filter, and dry at -5 °C for 24 h to obtain a sustained-release microcapsule; (3) Vacuum dry Sargassum horneri at 40 °C for 24 h, grind to 80 mesh, ultrasonicate at 65 °C and 450 W for 25 min, dry at -5 °C for 24 h, add a food-grade cellulase 0.04 times the mass of Sargassum horneri and 4 times the mass of deionized water of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, let stand at 65 °C for 8 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; Wash oyster shells 4 times with deionized water and grind to 90 mesh to obtain oyster shell powder; Take 5 parts of Sargassum horneri fertilizer, 2.5 parts of oyster shell powder, and 1.2 parts of sustained-release microcapsule by mass fraction. Mix the Sargassum horneri fertilizer, oyster shell powder, and sustained-release microcapsule to obtain a liquid fertilizer.

[0028] Test Example 4 A process for preparing liquid fertilizer from tilmicosin waste liquid mainly includes the following preparation steps: (1) Take 5 parts of deionized water, 0.225 parts of potassium hydroxide, 0.2 parts of stearic acid, 0.225 parts of triethanolamine, and 0.9 parts of citric acid by mass fraction. Mix the deionized water and potassium hydroxide, heat to 70 °C, add stearic acid, cool to 50 °C, add triethanolamine, stir at 125 r / min for 15 min, let stand for 60 min, cool to 30 °C, add citric acid, let stand for 3 h, and adjust the pH to 7 with 0.1 M potassium hydroxide aqueous solution to obtain a water repellent; take 1.5 parts of starch, 0.8 parts of low-polymerization-degree polyvinyl alcohol, 0.08 parts of sodium carboxymethyl cellulose, 7.5 parts of glycerol, 1 part of ammonia water, 0.2 parts of polyethylene glycol with a polymerization degree of 1200, 17.5 parts of deionized water, 2 parts of water repellent, and 1.85 parts of ethyl silicate by mass fraction. Mix the starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 95 °C and 250 r / min for 60 min, add ammonia water and ethyl silicate, and continue to stir for 30 min to obtain a film solution; (2) Mix graphene oxide and titanium dioxide in a mass ratio of 1:4, grind to 150 mesh, add methanol 5 times the mass of graphene oxide, ultrasonicate for 120 min, irradiate with light for 7 h at 250 r / min under a UV-B lamp and nitrogen protection, and dry at room temperature for 23 h to obtain a graphene oxide-titanium dioxide composite material; mix hollow mesoporous silica, deionized water, and Paenibacillus polymyxa in a mass ratio of 1:10:2.5, ultrasonicate at 2 °C for 30 min, let stand under vacuum conditions for 27.5 min, restore to normal pressure, repeat the operation 3 times, centrifuge at 5000 r / min for 5 min, wash 4 times with ethanol, and vacuum dry at -5 °C for 12 h, grind to 40 mesh to obtain modified hollow mesoporous silica; mix the tilmicosin waste liquid and the graphene oxide-titanium dioxide composite material in a mass ratio of 1:0.15, dry at 75 °C for 23 h to obtain a tilmicosin-loaded composite material; mix the tilmicosin-loaded composite material and mineral oil in a mass ratio of 1:0.15, stir at 250 r / min for 4 min, then add ethyl cellulose equal in mass to the mineral oil and modified hollow mesoporous silica equal in mass to the mineral oil, continue to stir for 4 min, pour into the film solution, filter, and dry at -5 °C for 24 h to obtain a sustained-release microcapsule; (3) Vacuum dry Sargassum horneri at 40 °C for 24 h, grind to 80 mesh, ultrasonicate at 65 °C and 450 W for 25 min, dry at -5 °C for 24 h, add food-grade cellulase 0.04 times the mass of Sargassum horneri and deionized water 4 times the mass of Sargassum horneri, adjust the pH to 4 with 0.1 M hydrochloric acid solution, let stand at 65 °C for 8 h, and adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; take 5 parts of Sargassum horneri fertilizer and 1.2 parts of sustained-release microcapsule by mass fraction, mix the Sargassum horneri fertilizer and the sustained-release microcapsule to obtain a liquid fertilizer.

[0029] Test Example 1: Photocatalytic degradation test of antibiotics: Weigh 300 mg of liquid fertilizer and place it in a beaker. Add 50 ml of deionized water and wrap the beaker tightly with tin foil. Conduct a 1-hour dark reaction. After the dark reaction, irradiate with a 300 W xenon lamp with a wavelength of 450 nm as the light source. After 6 hours, draw 4 ml of the sample from the reaction solution and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the absorbance of the sample and calculate the antibiotic concentration, denoted as C1. Weigh 300 mg of liquid fertilizer and place it in a beaker. Add 50 ml of deionized water and wrap the beaker tightly with tin foil. Conduct a 7-hour dark reaction. After the dark reaction, draw 4 ml of the sample from the reaction solution and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the absorbance of the sample and calculate the antibiotic concentration, denoted as C0; calculate the degradation rate, where the degradation rate = (C0 - C1) / C0 * 100%. The results are shown in Table 1.

[0030] Table 1

[0031] From the comparison of the experimental data in Table 1, it can be found that the liquid fertilizer prepared by the present invention has good ability to photocatalytically degrade antibiotics.

[0032] From the comparison of the experimental data of Examples 1, 2, 3, 4, 5 and Comparative Example 3 in Table 1, it can be found that the degradation rates of Examples 1, 2, 3, 4, 5 are larger than that of Comparative Example 3, indicating that an inorganic composite material capable of photocatalytically degrading tylosin can be prepared by mixing graphene oxide, methanol and titanium dioxide and irradiating with UV-B light.

[0033] Test Example 2: Sustained-release antibiotic test: Weigh 300 mg of liquid fertilizer and place it in a beaker. Add 50 ml of deionized water and wrap the beaker tightly with tin foil. Let it stand still for 3 hours under dark conditions. Draw 4 ml of the sample from the mixture and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the absorbance of the sample and calculate the antibiotic concentration, denoted as M0; let it stand still for 30 days under dark conditions. Draw 4 ml of the sample from the mixture and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the absorbance of the sample and calculate the antibiotic concentration, denoted as M1, and calculate the 1-day sustained-release rate = (M1 - M0) / M1 * 100%. The results are shown in Table 2.

[0034] Table 2

[0035] From the comparison of the experimental data in Table 2, it can be found that the liquid fertilizer prepared by the present invention has good ability to sustainably release antibiotics.

[0036] From the comparison of the experimental data of Examples 1, 2, 3, 4, 5 and Comparative Example 1 in Table 2, it can be found that the 1d sustained-release rates of Examples 1, 2, 3, 4, 5 are smaller than that of Comparative Example 1, indicating that attaching a polymer film to the surface of the tilmicosin composite material can achieve a sustained-release effect.

[0037] Test Example 3: Soil pH adjustment test: Mix the liquid fertilizer and soil with a pH of 5.3 evenly at a mass ratio of 1:50, put it into a ceramic pot for cultivation, supplement deionized water every 3 days during the cultivation period, and use the weighing method to keep the soil moisture content at 20%. After 20 days, detect the soil pH value. The results are shown in Table 3.

[0038] Table 3

[0039] From the comparison of the experimental data in Table 3, it can be found that the liquid fertilizer prepared by the present invention has good ability to adjust the soil pH.

[0040] From the comparison of the experimental data of Examples 1, 2, 3, 4, 5 and Comparative Example 4 in Table 3, it can be found that the pH values of Examples 1, 2, 3, 4, 5 are closer to neutral than that of Comparative Example 4, indicating that oyster shells can adjust the pH of acidic soil.

[0041] Test Example 4: Nitrogen fixation test: Use an ultraviolet-visible spectrometer to measure the nitrogen element content in the liquid fertilizer, denoted as M0; pour 300 mL of deionized water through 30 g of air-dried soil, let it stand for 3 days, pour 800 mL of deionized water over the soil, and use an ultraviolet-visible spectrometer to measure the nitrogen element content in the outflow liquid, denoted as M1; take 300 mL of the liquid fertilizer and pour it through 30 g of the same air-dried soil, let it stand for 3 days, pour 800 mL of deionized water over the soil, and use an ultraviolet-visible spectrometer to measure the nitrogen element content in the outflow liquid, denoted as M2, and calculate the nitrogen retention rate, where the nitrogen retention rate = (M2 - M1) / M0 * 100%. The results are shown in Table 4.

[0042] Table 4

[0043] From the comparison of the experimental data in Table 4, it can be found that the liquid fertilizer prepared by the present invention has good nitrogen fixation ability.

[0044] From the comparison of the experimental data of Examples 1, 2, 3, 4, 5 and Comparative Example 2 in Table 2, it can be found that the nitrogen retention rates of Examples 1, 2, 3, 4, 5 are larger than that of Comparative Example 2, indicating that Paenibacillus polymyxa is loaded inside the hollow mesoporous silica, and Paenibacillus polymyxa, as a nitrogen-fixing bacterium, can achieve a nitrogen fixation effect.

[0045] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A process for preparing liquid fertilizer from tylvalosin waste liquid, characterized in that, The process for preparing liquid fertilizer from the tilmicosin waste liquid is obtained by drying, grinding, ultrasonically treating Sargassum horneri, enzymatically hydrolyzing with cellulase, and mixing with slow-release microcapsules and oyster shell powder; The slow-release microcapsules are obtained by successively mixing the tilmicosin-loaded composite material with mineral oil, ethyl cellulose, and modified hollow mesoporous silica, and then pouring it into the membrane solution and drying; The modified hollow mesoporous silica is obtained by mixing hollow mesoporous silica, deionized water, and Paenibacillus polymyxa, evacuating, and then restoring to normal pressure, and repeating the operation; The membrane solution is obtained by mixing starch, low-polymerization-degree polyvinyl alcohol, sodium carboxymethyl cellulose, glycerol, ammonia water, polyethylene glycol, tetraethyl orthosilicate, deionized water, and a water repellent; The water repellent is obtained by reacting potassium hydroxide, stearic acid, triethanolamine, and citric acid; The tilmicosin-loaded composite material is obtained by mixing the tilmicosin waste liquid with graphene oxide-titanium dioxide composite material and drying; The graphene oxide-titanium dioxide composite material is obtained by mixing graphene oxide, methanol, and titanium dioxide and irradiating with UV-B lamp light; 2. The process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 1, characterized in that, The process for preparing liquid fertilizer from the tilmicosin waste liquid mainly includes the following preparation steps: (1) Take 4 - 6 parts by mass of deionized water, 0.2 - 0.25 parts by mass of potassium hydroxide, 0.15 - 0.25 parts by mass of stearic acid, 0.2 - 0.25 parts by mass of triethanolamine, and 0.8 - 1 part by mass of citric acid. Mix the deionized water and potassium hydroxide, heat to 65 - 75 °C, add stearic acid, cool to 45 - 55 °C, add triethanolamine, stir at 100 - 150 r / min for 10 - 20 min, let stand for 50 - 70 min, cool to 25 - 35 °C, add citric acid, let stand for 2 - 4 h, and adjust the pH to 6.5 - 7.5 with 0.1 M potassium hydroxide aqueous solution to obtain the water repellent; Take 1 - 2 parts by mass of starch, 0.7 - 0.9 parts by mass of low-polymerization-degree polyvinyl alcohol, 0.07 - 0.09 parts by mass of sodium carboxymethyl cellulose, 7 - 8 parts by mass of glycerol, 0.8 - 1.2 parts by mass of ammonia water, 0.15 - 0.25 parts by mass of polyethylene glycol, 17 - 18 parts by mass of deionized water, 1.8 - 2.2 parts by mass of the water repellent, and 1.8 - 1.9 parts by mass of tetraethyl orthosilicate. Mix starch, low-polymerization-degree polyvinyl alcohol, glycerol, polyethylene glycol, sodium carboxymethyl cellulose, and deionized water, stir at 90 - 100 °C and 200 - 300 r / min for 50 - 70 min, add ammonia water and tetraethyl orthosilicate, and continue stirring for 20 - 40 min to obtain the membrane solution; (2) Mix graphene oxide and titanium dioxide in a mass ratio of 1:3 - 5, grind to 130 - 170 mesh, add methanol in an amount 4 - 6 times the mass of graphene oxide, sonicate for 100 - 140 min, under 200 - 300 r / min, with a UV - B lamp and nitrogen protection, irradiate for 6 - 8 h, dry at room temperature for 22 - 24 h to obtain a graphene oxide - titanium dioxide composite material; Mix hollow mesoporous silica, deionized water and Paenibacillus polymyxa in a mass ratio of 1:8 - 12:2 - 3, sonicate at 0 - 4 °C for 25 - 35 min, let stand under vacuum conditions for 25 - 30 min, restore to normal pressure, repeat the operation 2 - 4 times, centrifuge at 5000 r / min for 4 - 6 min, wash with ethanol 3 - 5 times, vacuum dry at - 10 - 0 °C for 11 - 13 h, grind to 30 - 50 mesh to obtain modified hollow mesoporous silica; Mix the tilmicosin waste liquid and the graphene oxide - titanium dioxide composite material in a mass ratio of 1:0.1 - 0.2, dry at 70 - 80 °C for 22 - 24 h to obtain a tilmicosin - loaded composite material; Mix the tilmicosin - loaded composite material and mineral oil in a mass ratio of 1:0.1 - 0.2, stir at 200 - 300 r / min for 3 - 5 min, then add ethyl cellulose with the same mass as the mineral oil and modified hollow mesoporous silica with the same mass as the mineral oil, continue to stir for 3 - 5 min, pour into the membrane solution, filter, dry at - 10 - 0 °C for 22 - 26 h to obtain slow - release microcapsules; (3) Vacuum - dry Sargassum horneri at 30 - 50 °C for 22 - 26 h, grind to 60 - 100 mesh, sonicate at 60 - 70 °C and 400 - 500 W for 20 - 30 min, dry at - 10 - 0 °C for 22 - 26 h, add food - grade cellulase in an amount 0.03 - 0.05 times the mass of Sargassum horneri and deionized water in an amount 3 - 5 times the mass of Sargassum horneri, adjust the pH to 3.5 - 4.5 with 0.1 M hydrochloric acid solution, let stand at 60 - 70 °C for 7 - 9 h, adjust the pH to 7 with 0.1 M potassium acetate aqueous solution to obtain Sargassum horneri fertilizer; Wash oyster shells with deionized water 3 - 5 times, grind to 80 - 100 mesh to obtain oyster shell powder; Take 4 - 6 parts by mass of Sargassum horneri fertilizer, 2 - 3 parts by mass of oyster shell powder, and 1 - 1.4 parts by mass of slow - release microcapsules, mix the Sargassum horneri fertilizer, oyster shell powder and slow - release microcapsules to obtain a liquid fertilizer.

3. A process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The ammonia water described in step (1) is industrial - grade ammonia water.

4. A process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The starch described in step (1) is industrial - grade pre - gelatinized starch.

5. The process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The degree of polymerization of the polyethylene glycol described in step (1) is 1000 - 1400.

6. The process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The sodium carboxymethyl cellulose described in step (1) is food - grade sodium carboxymethyl cellulose.

7. A process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The glycerol described in step (1) is industrial - grade glycerol.

8. A process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The hollow mesoporous silica described in step (2) is hollow mesoporous silica with a purity greater than 99.9%.

9. The process for preparing liquid fertilizer from tilmicosin waste liquid according to claim 2, characterized in that, The Paenibacillus polymyxa described in step (2) is a water - soluble Paenibacillus polymyxa.

10. A process for preparing liquid fertilizer from tylvalosin waste liquid according to claim 2, characterized in that, The mineral oil described in step (2) is industrial white mineral oil.

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