Method for preparing liquid fertilizer from ivermectin waste liquid

Abstract

The invention discloses a method for preparing a liquid fertilizer from ivermectin waste liquid, and relates to the field of fertilizers. When the ivermectin waste liquid is used for preparing the liquid fertilizer, chitin and phosphoric acid are mixed, filtered and washed, and regenerated chitin is prepared; mixing regenerated chitin and deionized water, homogenizing, mixing with ivermectin mixed liquor, dispersing, and reacting with ethylenediamine to prepare a pre-modified sustained-release microcapsule; enabling the pre-modified sustained-release microcapsule, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide to react, so as to prepare a modified sustained-release microcapsule; the preparation method comprises the following steps: alkalizing chitosan, and reacting with monochloroacetic acid to prepare a water-retaining agent; the preparation method comprises the following steps: drying kelp, grinding, carrying out ultrasonic treatment, carrying out enzymolysis with papain, and mixing with the modified slow-release microcapsule and the water-retaining agent to prepare the liquid fertilizer. The liquid fertilizer prepared by the invention has good effects of slow release, photodegradation of ivermectin and water retention.

Description

Technical Field

[0001] The invention relates to the field of fertilizers, in particular to a method for preparing liquid fertilizer from ivermectin waste liquid. Background Art

[0002] Seaweed fertilizer is a kind of biological organic fertilizer made from marine algae by chemical, physical or biological methods to extract biologically active substances from seaweed. Seaweed fertilizer is a natural organic fertilizer. Since seaweed grows in the special environment of seawater, it also contains seaweed polysaccharides, alginate, highly unsaturated fatty acids unique to marine organisms, as well as more than 40 kinds of minerals and rich vitamins that general terrestrial plants do not have. Applying it to crops and vegetables can promote plant growth, increase crop yields, improve the quality of agricultural products, and enhance the ability of crops to resist adverse environments.

[0003] With the development of human society, resource consumption is increasing, and the recycling of waste resources has become a hot topic of concern. Antibiotic wastewater is very harmful to the environment and human body. First, antibiotic wastewater can cause water pollution, destroy the water ecological balance, and affect water quality. Secondly, antibiotic wastewater can also cause soil pollution, causing agricultural products to contain antibiotic residues, posing a threat to human health. In order to solve the harm of antibiotic wastewater to the environment and human body and recycle waste resources, this article introduces a method for preparing liquid fertilizer from ivermectin waste liquid that can slowly release and decompose ivermectin waste liquid. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing liquid fertilizer from ivermectin waste liquid, so as to solve the problems existing in the prior art.

[0005] A method for preparing liquid fertilizer from ivermectin waste liquid, wherein the method comprises sequentially reacting polyester with epichlorohydrin, modified nano silicon dioxide and 4-aminobenzyl diethyl phosphate to obtain modified polyester, and spinning the polyester to obtain liquid fertilizer; The polyester is prepared by reacting octamethylcyclotetrasiloxane, 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane and 3-dimethylaminopropyl(dimethoxy)methylsilane, and then reacting with dimethyl terephthalate and ethylene glycol; The modified nano-silica is prepared by first reacting 1-allyl-1H-pyrrole with trimethoxysilane and nano-silica, and then reacting with pyrrole, 1-aminopyrrole and functional pyrrole monomers; The functional pyrrole monomer is prepared by hydrolyzing 2-hydroxy-4-(1H-pyrrol-1-yl) methyl benzoate and then reacting it with 1,2-phenylenediamine.

[0006] As an optimization, the method for preparing liquid fertilizer from ivermectin waste liquid mainly includes the following preparation steps: (1) Mix chitosan and deionized water in a mass ratio of 1:2.5~3.5, let stand for 25~35 minutes, add 45~55 times the mass of chitosan in a phosphoric acid aqueous solution, stir at 25~35°C, 200~300r / min for 100~140min, pour into deionized water, let stand for 50~70min, filter, and wash with deionized water until neutral to obtain regenerated chitosan; mix regenerated chitosan and deionized water in a mass ratio of 1:4~6, homogenize with a high-speed shearing machine at 9000~11000r / min for 50~70s to obtain a regenerated chitosan suspension; mix the ivermectin mixture with the regenerated chitosan suspension in a mass ratio of 1:1 Mix, disperse with a high-speed shearing machine at 55-65°C and 9000-11000 r / min for 2-4 min, add a dilute ethylenediamine aqueous solution at a rate of 0.3-0.5 times the mass of the regenerated chitin suspension at a uniform rate within 8-10 min, react at 55-65°C and 200-300 r / min for 100-140 min, add a concentrated ethylenediamine aqueous solution at a rate of 0.2-0.3 times the mass of the regenerated chitin suspension at a uniform rate within 8-10 min, heat to 65-75°C, continue stirring for 5-7 h, cool to room temperature, filter, wash with deionized water 3-5 times, and dry at -10-0°C for 22-24 h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.15-0.25:0.66-0.7:2.6-3, stirred at 200-300 r / min for 25-35 min, transferred to a polyvinyl fluoride liner, reacted at 100-120°C for 18-22 h, washed with ethanol for 3-5 times, and dried to obtain modified sustained-release microcapsules; (3) Mix chitosan, sodium hydroxide and isopropanol in a mass ratio of 1:1.3-1.7:3-5, stir at 200-300 r / min for 100-140 min, add monochloroacetic acid solution 2-3 times the mass of chitosan, continue stirring at 20-30°C for 2.5-3.5 h, filter, wash with ethanol 3-5 times, and vacuum dry at 60-70°C for 8-12 h to obtain a water retaining agent; (4) Dry the kelp in vacuum at 30-50°C for 22-26 h, grind to 60-100 mesh, ultrasonicate at 60-70°C and 400-500W for 20-30 min, dry at -10-0°C for 22-26 h, add papain (0.03-0.05 times the mass of the kelp) and deionized water (3-5 times the mass of the kelp), and let stand at 70-80°C for 7-9 h to prepare kelp fertilizer; take 4-6 parts of kelp fertilizer, 1-1.4 parts of modified slow-release microcapsules, and 0.8-1 parts of water retaining agent by mass, mix the kelp fertilizer, modified slow-release microcapsules and water retaining agent to prepare liquid fertilizer.

[0007] As an optimization, the phosphoric acid aqueous solution in step (1) is a phosphoric acid aqueous solution with a mass fraction of 85%.

[0008] As an optimization, the ivermectin mixed solution in step (1) is obtained by drying the ivermectin waste liquid at 60-70° C. for 56-60 hours to obtain ivermectin waste residue, and then uniformly mixing the ivermectin waste residue with ethyl acetate in a mass ratio of 1:3-5.

[0009] As an optimization, the dilute ethylenediamine aqueous solution in step (1) is a 2 wt % ethylenediamine aqueous solution.

[0010] As an optimization, the concentrated ethylenediamine aqueous solution in step (1) is a 10 wt% ethylenediamine aqueous solution.

[0011] As an optimization, the specific operation of drying in step (2) is drying at -10~0°C for 22~24h.

[0012] As an optimization, the chitosan in step (3) is food grade water-soluble chitosan.

[0013] As an optimization, the monochloroacetic acid solution in step (3) is prepared by uniformly mixing monochloroacetic acid and isopropanol in a mass ratio of 1:4-6.

[0014] As an optimization, the papain in step (4) is food grade papain.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing ivermectin waste liquid to prepare liquid fertilizer, the present invention comprises the following steps: mixing chitosan with phosphoric acid, filtering and washing to obtain regenerated chitosan; mixing the regenerated chitosan with deionized water, homogenizing, mixing with ivermectin mixed liquid, dispersing, and reacting with ethylenediamine to obtain pre-modified slow-release microcapsules; reacting the pre-modified slow-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide to obtain modified slow-release microcapsules; alkalizing chitosan, and reacting with monochloroacetic acid to obtain a water-retaining agent; and drying, grinding, ultrasonicating, enzymolyzing with papain, and mixing with the modified slow-release microcapsules and the water-retaining agent to obtain liquid fertilizer.

[0016] First, chitosan is mixed with phosphoric acid, filtered, and washed to obtain regenerated chitosan; the regenerated chitosan is mixed with deionized water, homogenized, mixed with an ivermectin mixed solution, dispersed, and then reacted with ethylenediamine to obtain pre-modified sustained-release microcapsules; the regenerated chitosan is reacted with ethylenediamine to generate a polyurea shell with a sustained-release effect, which is wrapped on the surface of ivermectin to achieve the effect of sustained-release ivermectin.

[0017] The pre-modified slow-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide are reacted to prepare modified slow-release microcapsules; chitosan is alkalized and then reacted with monochloroacetic acid to prepare a water-retaining agent; the kelp is dried, ground, ultrasonicated, enzymatically hydrolyzed with papain, and mixed with the modified slow-release microcapsules and the water-retaining agent to prepare liquid fertilizer; the surface of the pre-modified slow-release microcapsules is rich in amino groups, which can react with ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide to prepare iron-based MOF materials, which can degrade the slowly released ivermectin under photocatalytic conditions and avoid antibiotic pollution of the environment; chitosan is alkalized and then reacted with monochloroacetic acid to make it a polymer rich in hydrophilic groups with a porous structure, which plays the role of a water-retaining agent. DETAILED DESCRIPTION

[0018] 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.

[0019] Embodiment 1: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 60°C for 56 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was mixed with ethyl acetate at a mass ratio of 1:3 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water at a mass ratio of 1:2.5, allowed to stand for 25 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 45 times the mass of chitosan was added, stirred at 25°C and 200 r / min for 100 minutes, poured into deionized water, allowed to stand for 50 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed at a mass ratio of 1:4, and uniformly shredded with a high-speed shearing machine at 9000 r / min. The mixture was massed for 50 seconds to obtain a regenerated chitosan suspension; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 55°C and 9000 r / min for 2 minutes using a high-speed shearing machine, 0.3 times the mass of the regenerated chitosan suspension in a 2wt% aqueous solution of ethylenediamine was added at a uniform speed within 8, reacted at 55°C and 200 r / min for 100 minutes, 0.2 times the mass of the regenerated chitosan suspension in a 10wt% aqueous solution of ethylenediamine was added at a uniform speed within 8, the temperature was raised to 65°C, stirring was continued for 5 hours, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried at -10°C for 22 hours to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.15:0.66:2.6, stirred at 200 r / min for 25 min, transferred to a polyvinyl fluoride liner, reacted at 100 °C for 18 h, washed with ethanol three times, and dried at -10 °C for 22 h to obtain modified sustained-release microcapsules; (3) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:4 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.3:3, stirred at 200 r / min for 100 min, monochloroacetic acid solution twice the mass of chitosan was added, stirring was continued at 20°C for 2.5 h, filtered, washed with ethanol 3 times, and vacuum dried at 60°C for 8 h to obtain a water retaining agent; (4) The kelp was vacuum dried at 30°C for 22 h, ground into 60 mesh, ultrasonically treated at 60°C, 400 W for 20 min, dried at -10°C for 22 h, added with papain (0.03 times the mass of the kelp) and deionized water (3 times the mass of the kelp), and allowed to stand at 70°C for 7 h to obtain kelp fertilizer; 4 parts of kelp fertilizer, 1 part of modified slow-release microcapsules, and 0.8 parts of water retaining agent were taken by mass, and the kelp fertilizer, modified slow-release microcapsules, and water retaining agent were mixed to obtain liquid fertilizer.

[0020] Embodiment 2: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 70°C for 56 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was evenly mixed with ethyl acetate in a mass ratio of 1:4 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water in a mass ratio of 1:3, allowed to stand for 25 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 50 times the mass of chitosan was added, stirred at 35°C and 250 r / min for 100 minutes, poured into deionized water, allowed to stand for 50 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed in a mass ratio of 1:5, and homogenized with a high-speed shearing machine at 10000 r / min for 50 seconds. , to obtain a regenerated chitosan suspension; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 65°C, 10000r / min for 2min using a high-speed shearing machine, and a 2wt% aqueous solution of ethylenediamine in an amount of 0.4 times the mass of the regenerated chitosan suspension was uniformly added within 8min, reacted at 65°C, 250r / min for 100min, and a 10wt% aqueous solution of ethylenediamine in an amount of 0.25 times the mass of the regenerated chitosan suspension was uniformly added within 8min, the temperature was raised to 75°C, stirring was continued for 5h, cooled to room temperature, filtered, washed with deionized water 4 times, and dried at 0°C for 22h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.2:0.68:2.8, stirred at 250 r / min for 25 min, transferred to a polyvinyl fluoride liner, reacted at 120°C for 18 h, washed with ethanol 4 times, and dried at 0°C for 22 h to obtain modified sustained-release microcapsules; (3) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:5 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.5:4, stirred at 250 r / min for 100 min, monochloroacetic acid solution 2.5 times the mass of chitosan was added, stirring was continued at 30°C for 2.5 h, filtered, washed with ethanol 4 times, and vacuum dried at 70°C for 8 h to obtain a water retaining agent; (4) The kelp was vacuum dried at 50°C for 22 h, ground into 80 mesh, ultrasonically treated at 70°C, 450W for 20 min, dried at 0°C for 22 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 80°C for 8 h to obtain kelp fertilizer; 5 parts of kelp fertilizer, 1.2 parts of modified slow-release microcapsules, and 0.9 parts of water retaining agent were taken by mass, and the kelp fertilizer, modified slow-release microcapsules, and water retaining agent were mixed to obtain liquid fertilizer.

[0021] Embodiment 3: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 65°C for 58 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was evenly mixed with ethyl acetate in a mass ratio of 1:4 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water in a mass ratio of 1:3, allowed to stand for 30 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 50 times the mass of chitosan was added, stirred at 30°C and 250 r / min for 120 minutes, poured into deionized water, allowed to stand for 60 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed in a mass ratio of 1:5, and homogenized with a high-speed shearing machine at 10000 r / min for 60 seconds. , to obtain a regenerated chitosan suspension; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 60°C and 10000r / min for 3min using a high-speed shearing machine, and a 2wt% aqueous solution of ethylenediamine in an amount of 0.4 times the mass of the regenerated chitosan suspension was uniformly added within 9min, reacted at 60°C and 250r / min for 120min, and a 10wt% aqueous solution of ethylenediamine in an amount of 0.25 times the mass of the regenerated chitosan suspension was uniformly added within 9min, the temperature was raised to 70°C, stirring was continued for 6h, cooled to room temperature, filtered, washed with deionized water 4 times, and dried at -5°C for 23h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.2:0.68:2.8, stirred at 250 r / min for 30 min, transferred to a polyvinyl fluoride liner, reacted at 110°C for 20, washed with ethanol 4 times, and dried at -5°C for 23 h to obtain modified sustained-release microcapsules; (3) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:5 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.5:4, stirred at 250 r / min for 120 min, monochloroacetic acid solution 2.5 times the mass of chitosan was added, stirring was continued at 25°C for 3 h, filtered, washed with ethanol 4 times, and vacuum dried at 65°C for 10 h to obtain a water retaining agent; (4) The kelp was vacuum dried at 40°C for 24 h, ground into 80 mesh, ultrasonically treated at 65°C, 450 W for 25 min, dried at -5°C for 24 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 75°C for 8 h to obtain kelp fertilizer; 5 parts of kelp fertilizer, 1.2 parts of modified slow-release microcapsules, and 0.9 parts of water retaining agent were taken by mass, and the kelp fertilizer, modified slow-release microcapsules, and water retaining agent were mixed to obtain liquid fertilizer.

[0022] Embodiment 4: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 60°C for 60 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was evenly mixed with ethyl acetate at a mass ratio of 1:4 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water at a mass ratio of 1:3, allowed to stand for 35 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 50 times the mass of chitosan was added, stirred at 25°C and 25 r / min for 140 minutes, poured into deionized water, allowed to stand for 70 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed at a mass ratio of 1:5, and homogenized with a high-speed shearing machine at 10000 r / min for 70 seconds. A regenerated chitosan suspension was obtained; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 55°C and 10000 r / min for 4 min using a high-speed shearing machine, 0.4 times the mass of the regenerated chitosan suspension in a 2wt% aqueous solution of ethylenediamine was uniformly added within 10 min, reacted at 55°C and 250 r / min for 140 min, 0.25 times the mass of the regenerated chitosan suspension in a 10wt% aqueous solution of ethylenediamine was uniformly added within 10 min, the temperature was raised to 65°C, stirring was continued for 6 h, cooled to room temperature, filtered, washed with deionized water 4 times, and dried at 0°C for 24 h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.2:0.68:2.8, stirred at 250 r / min for 35 min, transferred to a polyvinyl fluoride liner, reacted at 100 °C for 22 h, washed with ethanol 4 times, and dried at -10 °C for 24 h to obtain modified sustained-release microcapsules; (3) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:5 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.5:4, stirred at 250 r / min for 140 min, monochloroacetic acid solution 2.5 times the mass of chitosan was added, stirring was continued at 20°C for 3.5 h, filtered, washed with ethanol 4 times, and vacuum dried at 60°C for 12 h to obtain a water retaining agent; (4) The kelp was vacuum dried at 30°C for 26 h, ground into 80 mesh, ultrasonically treated at 60°C, 450W for 30 min, dried at -10°C for 26 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 70°C for 9 h to obtain kelp fertilizer; 5 parts of kelp fertilizer, 1.2 parts of modified slow-release microcapsules, and 0.9 parts of water retaining agent were taken by mass, and the kelp fertilizer, modified slow-release microcapsules, and water retaining agent were mixed to obtain liquid fertilizer.

[0023] Embodiment 5: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) Dry the ivermectin waste liquid at 70°C for 60 hours to obtain ivermectin waste residue, and then mix the ivermectin waste residue with ethyl acetate at a mass ratio of 1:5 to obtain an ivermectin mixed solution; mix chitosan with deionized water at a mass ratio of 1:3.5, let it stand for 35 minutes, add 85% phosphoric acid aqueous solution 55 times the mass of chitosan, stir at 35°C and 300 r / min for 140 minutes, pour into deionized water, let it stand for 70 minutes, filter, and wash with deionized water until neutral to obtain regenerated chitosan; mix the regenerated chitosan with deionized water at a mass ratio of 1:6, and homogenize with a high-speed shearing machine at 11000 r / min for 70 seconds. A regenerated chitosan suspension was obtained; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 65°C and 11000 r / min for 4 min using a high-speed shearing machine, 0.5 times the mass of the regenerated chitosan suspension was uniformly added with a 2wt% aqueous solution of ethylenediamine within 10 min, reacted at 65°C and 300 r / min for 140 min, 0.3 times the mass of the regenerated chitosan suspension was uniformly added with a 10wt% aqueous solution of ethylenediamine within 10 min, the temperature was raised to 75°C, stirring was continued for 7 h, cooled to room temperature, filtered, washed with deionized water for 5 times, and dried at 0°C for 24 h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.25:0.7:3, stirred at 300 r / min for 35 min, transferred to a polyvinyl fluoride liner, reacted at 120°C for 22 h, washed with ethanol 5 times, and dried at 0°C for 24 h to obtain modified sustained-release microcapsules; (3) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:6 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.7:5, stirred at 300 r / min for 140 min, and a monochloroacetic acid solution 3 times the mass of chitosan was added, and the mixture was stirred at 30°C for 3.5 h, filtered, washed with ethanol 5 times, and vacuum dried at 70°C for 12 h to obtain a water retaining agent; (4) The kelp was vacuum dried at 50°C for 26 h, ground into 100 mesh, ultrasonically treated at 70°C, 500 W for 30 min, dried at 0°C for 26 h, added with papain (0.05 times the mass of the kelp) and deionized water (5 times the mass of the kelp), and allowed to stand at 80°C for 9 h to obtain kelp fertilizer; 6 parts of kelp fertilizer, 1.4 parts of pre-modified slow-release microcapsules, and 1 part of water retaining agent were taken by mass, and the kelp fertilizer, modified slow-release microcapsules and water retaining agent were mixed to obtain liquid fertilizer.

[0024] Comparative Example 1: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 65°C for 58 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was evenly mixed with ethyl acetate in a mass ratio of 1:4 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water in a mass ratio of 1:3, allowed to stand for 30 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 50 times the mass of chitosan was added, stirred at 30°C and 250 r / min for 120 minutes, poured into deionized water, allowed to stand for 60 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed in a mass ratio of 1:5, and homogenized with a high-speed shearing machine at 10000 r / min for 60 seconds. , to obtain a regenerated chitosan suspension; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 60°C and 10000r / min for 3min using a high-speed shearing machine, and a 2wt% aqueous solution of ethylenediamine in an amount of 0.4 times the mass of the regenerated chitosan suspension was uniformly added within 9min, reacted at 60°C and 250r / min for 120min, and a 10wt% aqueous solution of ethylenediamine in an amount of 0.25 times the mass of the regenerated chitosan suspension was uniformly added within 9min, the temperature was raised to 70°C, stirring was continued for 6h, cooled to room temperature, filtered, washed with deionized water 4 times, and dried at -5°C for 23h to obtain pre-modified sustained-release microcapsules; (2) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:5 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.5:4, stirred at 250 r / min for 120 min, monochloroacetic acid solution 2.5 times the mass of chitosan was added, stirring was continued at 25°C for 3 h, filtered, washed with ethanol 4 times, and vacuum dried at 65°C for 10 h to obtain a water retaining agent; (3) The kelp was vacuum dried at 40°C for 24 h, ground into 80 mesh, ultrasonicated at 65°C, 450W for 25 min, dried at -5°C for 24 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 75°C for 8 h to obtain kelp fertilizer; 5 parts of kelp fertilizer, 1.2 parts of modified slow-release microcapsules, and 0.9 parts of water retaining agent were taken by mass, and the kelp fertilizer, pre-modified slow-release microcapsules and water retaining agent were mixed to obtain liquid fertilizer.

[0025] Comparative Example 2: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid is dried at 65°C for 58 hours to obtain ivermectin waste residue; (2) Monochloroacetic acid and isopropanol were mixed uniformly in a mass ratio of 1:5 to obtain a monochloroacetic acid solution; chitosan, sodium hydroxide and isopropanol were mixed in a mass ratio of 1:1.5:4, stirred at 250 r / min for 120 min, monochloroacetic acid solution 2.5 times the mass of chitosan was added, stirring was continued at 25°C for 3 h, filtered, washed with ethanol 4 times, and vacuum dried at 65°C for 10 h to obtain a water retaining agent; (3) The kelp was vacuum dried at 40°C for 24 h, ground into 80 mesh, ultrasonically treated at 65°C, 450W for 25 min, dried at -5°C for 24 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 75°C for 8 h to obtain kelp fertilizer; 5 parts of kelp fertilizer, 1.2 parts of ivermectin waste residue, and 0.9 parts of water retaining agent were taken by mass, and the kelp fertilizer, ivermectin waste residue, and water retaining agent were mixed to obtain liquid fertilizer.

[0026] Comparative Example 3: A method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) The ivermectin waste liquid was dried at 65°C for 58 hours to obtain ivermectin waste residue, and then the ivermectin waste residue was evenly mixed with ethyl acetate in a mass ratio of 1:4 to obtain an ivermectin mixed solution; chitosan was mixed with deionized water in a mass ratio of 1:3, allowed to stand for 30 minutes, and an 85% phosphoric acid aqueous solution with a mass fraction of 50 times the mass of chitosan was added, stirred at 30°C and 250 r / min for 120 minutes, poured into deionized water, allowed to stand for 60 minutes, filtered, and washed with deionized water until neutral to obtain regenerated chitosan; the regenerated chitosan and deionized water were mixed in a mass ratio of 1:5, and homogenized with a high-speed shearing machine at 10000 r / min for 60 seconds. , to obtain a regenerated chitosan suspension; the ivermectin mixed solution and the regenerated chitosan suspension were mixed in a mass ratio of 1:1, dispersed at 60°C and 10000r / min for 3min using a high-speed shearing machine, and a 2wt% aqueous solution of ethylenediamine in an amount of 0.4 times the mass of the regenerated chitosan suspension was uniformly added within 9min, reacted at 60°C and 250r / min for 120min, and a 10wt% aqueous solution of ethylenediamine in an amount of 0.25 times the mass of the regenerated chitosan suspension was uniformly added within 9min, the temperature was raised to 70°C, stirring was continued for 6h, cooled to room temperature, filtered, washed with deionized water 4 times, and dried at -5°C for 23h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.2:0.68:2.8, stirred at 250 r / min for 30 min, transferred to a polyvinyl fluoride liner, reacted at 110°C for 20, washed with ethanol 4 times, and dried at -5°C for 23 h to obtain modified sustained-release microcapsules; (3) The kelp was vacuum dried at 40°C for 24 h, ground into 80 mesh, ultrasonically treated at 65°C, 450 W for 25 min, dried at -5°C for 24 h, added with papain (0.04 times the mass of the kelp) and deionized water (4 times the mass of the kelp), and allowed to stand at 75°C for 8 h to obtain kelp fertilizer; 5 parts of kelp fertilizer and 1.2 parts of modified slow-release microcapsules were taken by mass, and the kelp fertilizer and the modified slow-release microcapsules were mixed to obtain liquid fertilizer.

[0027] Test Example 1: Water retention test: 100.0 g of 20 mesh sandy loam was mixed with 10 g of liquid fertilizer and transferred into a plastic tube with a diameter of 5.0 cm and a length of 30.0 cm. The weight was recorded as m 1 Next, slowly drip deionized water into the bottle until water seeps out of the soil. After hanging for a while until no water drips out, weigh the tube. 2 , place at 25℃ for 15 days, record the weight of the tube as m 3 , calculate the water retention rate, where water retention rate = (m 3 -m1 ) / (m 2 -m 1 )*100%The results are shown in Table 1.

[0028] Table 1 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 water retention capacity.

[0029] 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 water retention rates of Examples 1, 2, 3, 4, 5 are greater than that of Comparative Example 3, which indicates that chitosan is alkalized and then reacted with monochloroacetic acid to form a polymer with a porous structure and rich in hydrophilic groups, which plays the role of a water retaining agent.

[0030] Test Example 2: Photocatalytic degradation of antibiotics test: Weigh 300 mg of liquid fertilizer and place it in a beaker, add 50 ml of deionized water, wrap the beaker tightly with tin foil, and perform a dark reaction for 1 hour. After the dark reaction, irradiate with a 300W xenon lamp with a wavelength of 450 nm as the light source. After 6 hours, draw 4 ml of sample from the reaction solution and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the sample absorbance and calculate the antibiotic concentration, which is recorded as C1. Weigh 300 mg of liquid fertilizer and place it in a beaker, add 50 ml of deionized water, wrap the beaker tightly with tin foil, and perform a dark reaction for 7 hours. After the dark reaction, draw 4 ml of sample from the reaction solution and filter it with a 0.22 μm filter head. Use a UV-visible spectrophotometer to measure the sample absorbance and calculate the antibiotic concentration, which is recorded as C0. Calculate the degradation rate, where the degradation rate = (C0-C1) / C0*100%. The results are shown in Table 2.

[0031] Table 2 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 photocatalytic degradation ability of antibiotics.

[0032] 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 degradation rates of Examples 1, 2, 3, 4, 5 are greater than those of Comparative Example 1, indicating that the surface of the pre-modified sustained-release microcapsules is rich in amino groups, which can be reacted with ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide to prepare iron-based MOF materials, and the sustained-release ivermectin can be degraded under photocatalytic conditions, thereby avoiding antibiotic pollution of the environment.

[0033] Test Example 3: Sustained-release antibiotic testing: Weigh 300 mg of liquid fertilizer and place it in a beaker, add 50 ml of deionized water, wrap the beaker tightly with tin foil, let it stand for 1 day in the dark, draw 4 ml of sample from the mixed solution and filter it with a 0.22 μm filter head, use a UV-visible spectrophotometer to measure the sample absorbance, calculate the antibiotic concentration, and record it as M0; let it stand for 30 days in the dark, draw 4 ml of sample from the mixed solution and filter it with a 0.22 μm filter head, use a UV-visible spectrophotometer to measure the sample absorbance, calculate the antibiotic concentration, and record it as M1, and calculate the 1d sustained release rate = (M1-M0) / M1*100%. The results are shown in Table 3.

[0034] Table 3 From the comparison of the experimental data in Table 3, it can be found that the liquid fertilizer prepared by the present invention has a good ability to slowly release antibiotics.

[0035] From the comparison of the experimental data of Examples 1, 2, 3, 4, 5 and Comparative Example 2 in Table 3, it can be found that the 1d sustained release rate of Examples 1, 2, 3, 4, 5 is smaller than that of Comparative Example 2, which indicates that chitosan is mixed with phosphoric acid, filtered, and washed to obtain regenerated chitosan; the regenerated chitosan is mixed with deionized water, homogenized, mixed with the ivermectin mixed solution, dispersed, and then reacted with ethylenediamine to obtain pre-modified sustained-release microcapsules; the regenerated chitosan is reacted with ethylenediamine to generate a polyurea shell with a sustained-release effect, which is wrapped on the surface of ivermectin to achieve the effect of sustained-release ivermectin.

[0036] 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 method for preparing liquid fertilizer from ivermectin waste liquid, characterized in that: The method for preparing liquid fertilizer from ivermectin waste liquid is to sequentially react polyester with epichlorohydrin, modified nano silicon dioxide and 4-aminobenzyl diethyl phosphate to obtain modified polyester, and then spin the polyester to obtain liquid fertilizer; The polyester is prepared by reacting octamethylcyclotetrasiloxane, 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane and 3-dimethylaminopropyl(dimethoxy)methylsilane, and then reacting with dimethyl terephthalate and ethylene glycol; The modified nano-silica is prepared by first reacting 1-allyl-1H-pyrrole with trimethoxysilane and nano-silica, and then reacting with pyrrole, 1-aminopyrrole and functional pyrrole monomers; The functional pyrrole monomer is prepared by hydrolyzing 2-hydroxy-4-(1H-pyrrol-1-yl) methyl benzoate and then reacting it with 1,2-phenylenediamine.

2. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: The method for preparing liquid fertilizer from ivermectin waste liquid mainly comprises the following preparation steps: (1) Mix chitosan and deionized water in a mass ratio of 1:2.5~3.5, let stand for 25~35 minutes, add 45~55 times the mass of chitosan in a phosphoric acid aqueous solution, stir at 25~35°C, 200~300r / min for 100~140min, pour into deionized water, let stand for 50~70min, filter, and wash with deionized water until neutral to obtain regenerated chitosan; mix regenerated chitosan and deionized water in a mass ratio of 1:4~6, homogenize with a high-speed shearing machine at 9000~11000r / min for 50~70s to obtain a regenerated chitosan suspension; mix the ivermectin mixture with the regenerated chitosan suspension in a mass ratio of 1:1 Mix, disperse with a high-speed shearing machine at 55-65°C and 9000-11000 r / min for 2-4 min, add a dilute ethylenediamine aqueous solution at a rate of 0.3-0.5 times the mass of the regenerated chitin suspension at a uniform rate within 8-10 min, react at 55-65°C and 200-300 r / min for 100-140 min, add a concentrated ethylenediamine aqueous solution at a rate of 0.2-0.3 times the mass of the regenerated chitin suspension at a uniform rate within 8-10 min, heat to 65-75°C, continue stirring for 5-7 h, cool to room temperature, filter, wash with deionized water 3-5 times, and dry at -10-0°C for 22-24 h to obtain pre-modified sustained-release microcapsules; (2) Pre-modified sustained-release microcapsules, ferric chloride hexahydrate, 2-aminoterephthalic acid and dimethylformamide were mixed in a mass ratio of 1:0.15-0.25:0.66-0.7:2.6-3, stirred at 200-300 r / min for 25-35 min, transferred to a polyvinyl fluoride liner, reacted at 100-120°C for 18-22 h, washed with ethanol for 3-5 times, and dried to obtain modified sustained-release microcapsules; (3) Mix chitosan, sodium hydroxide and isopropanol in a mass ratio of 1:1.3-1.7:3-5, stir at 200-300 r / min for 100-140 min, add monochloroacetic acid solution 2-3 times the mass of chitosan, continue stirring at 20-30°C for 2.5-3.5 h, filter, wash with ethanol 3-5 times, and vacuum dry at 60-70°C for 8-12 h to obtain a water retaining agent; (4) Dry the kelp in vacuum at 30-50°C for 22-26 h, grind to 60-100 mesh, ultrasonicate at 60-70°C and 400-500W for 20-30 min, dry at -10-0°C for 22-26 h, add papain (0.03-0.05 times the mass of the kelp) and deionized water (3-5 times the mass of the kelp), and let stand at 70-80°C for 7-9 h to prepare kelp fertilizer; take 4-6 parts of kelp fertilizer, 1-1.4 parts of modified slow-release microcapsules, and 0.8-1 parts of water retaining agent by mass, mix the kelp fertilizer, modified slow-release microcapsules and water retaining agent to prepare liquid fertilizer.

3. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The phosphoric acid aqueous solution in step (1) is a phosphoric acid aqueous solution with a mass fraction of 85%.

4. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The ivermectin mixed solution in step (1) is obtained by drying ivermectin waste liquid at 60-70° C. for 56-60 hours to obtain ivermectin waste residue, and then uniformly mixing the ivermectin waste residue with ethyl acetate in a mass ratio of 1:3-5.

5. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The dilute ethylenediamine aqueous solution in step (1) is a 2 wt % ethylenediamine aqueous solution.

6. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The concentrated ethylenediamine aqueous solution in step (1) is a 10 wt % ethylenediamine aqueous solution.

7. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The specific operation of the drying in step (2) is drying at -10~0°C for 22~24h.

8. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The chitosan in step (3) is food grade water-soluble chitosan.

9. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The monochloroacetic acid solution in step (3) is prepared by uniformly mixing monochloroacetic acid and isopropanol in a mass ratio of 1:4-6.

10. The method for preparing liquid fertilizer from ivermectin waste liquid according to claim 2, characterized in that: The papain in step (4) is food grade papain.