Novel process for preparing liquid fertilizer from ivermectin waste liquid

Abstract

The invention discloses a novel process for preparing a liquid fertilizer from ivermectin waste liquid, and relates to the technical field of fertilizer preparation, aniline and acetic acid are used as raw materials, sulfuric acid catalytic esterification and nucleophilic substitution reaction with mercaptoethanol are performed to prepare a complexing agent, the complexing agent is added into the pretreated waste liquid, a reaction is performed to obtain a liquid fertilizer semi-finished product, and the liquid fertilizer semi-finished product is obtained. The preparation method comprises the following steps: mixing polyoxyethylene sorbitan fatty acid ester and sodium dodecyl benzene sulfonate, adding a buffer agent, stirring to prepare a compatibility regulator, adding the liquid fertilizer semi-finished product, and homogenizing to obtain the quasi-liquid fertilizer. According to the present invention, the liquid fertilizer is subjected to esterification reaction under the catalysis of sulfuric acid to construct the basic structure skeleton of the complexing agent so as to form the intermediate with the partial coordination ability, and the treated liquid fertilizer has characteristics of stable physicochemical property and strong compatibility after being mixed and stored with a variety of fertilizers and pesticides, such that the comprehensive application benefit in the agricultural production is substantially improved.

Description

Technical Field

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

[0002] Ivermectin is an antibiotic widely used in agriculture and animal husbandry. During its production process, a large amount of waste liquid is generated. This waste liquid contains various organic and inorganic components. If directly discharged without proper treatment, it will cause serious environmental pollution. At the same time, the demand for fertilizers in the agricultural field continues to grow. As a new type of fertilizer, liquid fertilizer has the advantages of convenient fertilization, fast absorption, and high utilization rate, and is gradually favored by farmers. Currently, the production raw materials of liquid fertilizer mainly come from chemical synthesis or fermentation treatment of animal and plant wastes, but these raw material sources have certain limitations, either with high costs or unstable supplies. Against this background, developing a novel process to convert ivermectin waste liquid into liquid fertilizer has important practical significance; There are certain defects in the existing technology. First, there is the problem of poor compatibility with other fertilizers or pesticides. In agricultural production, it is often necessary to mix liquid fertilizer with other fertilizers or pesticides to achieve the purposes of comprehensive fertilization and pest control. However, the liquid fertilizer prepared from existing ivermectin waste liquid may have poor compatibility with other commonly used agricultural inputs due to its special chemical composition and physical properties. After mixing, problems such as precipitation, flocculation, color change, reduced drug efficacy, or harmful chemical reactions may occur, restricting its flexible application and the exertion of comprehensive benefits in agricultural production. Second, there are problems of microbial growth and spoilage. The existing liquid fertilizer formulations and production processes do not consider anti-corrosion and antibacterial factors, and are prone to microbial growth during storage, resulting in fertilizer spoilage. The growth and reproduction of microorganisms not only consume the nutrients in the fertilizer, but may also produce harmful metabolites, change the chemical properties and physical states of the fertilizer, emit unpleasant odors, and reduce the quality and use value of the fertilizer. For this reason, we propose a novel process for preparing liquid fertilizer from ivermectin waste liquid. Summary of the Invention

[0003] The purpose of the present invention is to provide a novel process for preparing liquid fertilizer from ivermectin waste liquid.

[0004] To solve the problems raised in the above background art, the present invention provides the following technical solution: A novel process for preparing liquid fertilizer from ivermectin waste liquid, the process comprising the following specific steps: Step 1, Pretreatment of ivermectin waste liquid: Pour the ivermectin waste liquid into a reaction kettle, then start the stirring device to stir. After stirring is completed, filter and remove impurities using a filter screen. Then adjust the pH value of the waste liquid, and continue to stir after adjustment to complete the pretreatment of the ivermectin waste liquid; Step 2: Select aniline containing amino group and acetic acid containing carboxyl group as starting materials, carry out an esterification reaction using sulfuric acid as a catalyst to form an intermediate with partial coordination ability, and then slowly add the prepared intermediate into a reaction vessel containing mercaptoethanol, and at the same time add a basic catalyst triethylamine for a nucleophilic substitution reaction. During the reaction, a buffer solution is used to maintain the pH value of the reaction system, and a mercapto group is introduced into the reaction to obtain a complexing agent; Place the pretreated ivermectin waste liquid in a reaction kettle, slowly add the prepared complexing agent to the waste liquid, then start a stirring device at room temperature for low-speed stirring. After stirring for a period of time, gradually increase the stirring speed, and then increase the temperature of the reaction kettle for reaction to obtain a semi-finished liquid fertilizer; Step 3: Prepare a compatibility regulator. Mix the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate, then add a buffer to the mixture, and then place the mixed system in a high-speed stirrer at room temperature for a stirring reaction to obtain a compatibility regulator. Then slowly add the compatibility regulator to the semi-finished liquid fertilizer, and after adding, use a high-shear homogenizer to homogenize the mixed system to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator; Step 4: Use tetraethyl orthosilicate as a silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of ammonia water, and stir the reaction to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a silver nitrate solution and stir the reaction at room temperature to obtain nanoparticles loaded with silver ions. Subsequently, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) copolymer on the surface of the silver ion-loaded nanoparticles as a slow-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a dichloromethane solution of poly(lactic-co-glycolic acid), and then drop it into an aqueous phase containing polyvinyl alcohol, and then stir the reaction to form an emulsion to obtain intelligent antibacterial slow-release microspheres; Step 5: Plant triterpenoids prepared by the three major processes of Triple-MAX triple glycolysis, "Multi-Point" enzymatic oligopeptides, and "Bio-Synthesis biosynthesis". Add the prepared intelligent antibacterial slow-release microspheres and plant triterpenoids to the quasi-liquid fertilizer, and then carry out a low-speed stirring reaction to obtain the final liquid fertilizer.

[0005] As a further solution of the present invention: In the above step 1, after pouring the ivermectin waste liquid into the reaction kettle, start the stirring device, stir at a stirring speed of 100 r / min - 150 r / min for 30 min - 45 min, then filter and remove impurities using a filter screen with a pore size of 80 μm - 100 μm, and then use 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution to adjust the pH value to 7.0 - 8.0. After the adjustment is completed, continue to stir for 15 min - 20 min.

[0006] As a further aspect of the present invention: in the second step, the molar ratio of the starting materials aniline and acetic acid is 1:1.2 - 1.3, the concentration of the catalyst sulfuric acid is 98% - 99%, the esterification reaction is carried out at 80°C - 100°C for 4h - 6h, the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:1.5 - 2, the molar ratio of the added triethylamine to the intermediate is 0.1 - 0.2:1, and then the temperature is controlled at 60°C - 80°C to carry out the nucleophilic substitution reaction between the intermediate and mercaptoethanol, and the reaction time is controlled to be 3h - 5h. During the reaction process, a potassium dihydrogen phosphate - disodium hydrogen phosphate buffer solution is used to maintain the pH value of the reaction system at 6 - 7.

[0007] As a further aspect of the present invention: in the second step, the addition amount of the complexing agent is 2% - 3% of the waste liquid mass. Subsequently, the stirring device is started at room temperature, the initial stirring speed is set at 80r / min - 100r / min, and after continuously stirring for 20min - 30min, the stirring speed is gradually increased to 300r / min - 350r / min, and the temperature of the reaction kettle is raised to 50°C - 55°C. Under these conditions, the reaction is carried out for 2h - 3h. During the reaction process, the change in the concentration of the active ingredient in the waste liquid is monitored in real time by an on-line ultraviolet - visible spectrometer. When the monitored concentration of the active ingredient is reduced to less than 10% of the initial concentration, the reaction is stopped.

[0008] As a further aspect of the present invention: in the third step, polyoxyethylene sorbitan fatty acid ester and sodium dodecylbenzenesulfonate are mixed in a mass ratio of 2.5 - 3:1, the buffer is a potassium dihydrogen phosphate - disodium hydrogen phosphate buffer system, and they are mixed in a ratio adjusted to a pH value of 6.5 - 7.5. The stirring speed of the high-speed stirrer is 1500r / min - 2000r / min, and the stirring time is 45min - 60min to obtain a compatibility regulator.

[0009] As a further aspect of the present invention: in the third step, the addition amount of the compatibility regulator is 2.0% - 2.5% of the total mass of the liquid fertilizer semi-finished product, the rotation speed of the homogenizer is set at 4000r / min - 5000r / min, and the homogenization time is 8min - 10min.

[0010] As a further aspect of the present invention: in the fourth step, the concentration of ammonia water is 25% - 28%, and the molar ratio of tetraethyl orthosilicate, ethanol, water and ammonia water is 0.7 - 1:4:2:0.1. The reaction is stirred at 30°C - 33°C for 3h - 4h to form silicon dioxide nanoparticles.

[0011] As a further solution of the present invention: in the step four, the prepared silica nanoparticles are immersed in a silver nitrate solution with a concentration of 0.1 mol / L - 0.2 mol / L, and stirred at room temperature for 18 h - 20 h to obtain silver ion-loaded nanoparticles. The concentration of poly(lactic-co-glycolic acid) in dichloromethane solution is 10% - 15%, and the concentration of the aqueous phase of polyvinyl alcohol is 2% - 3%. Subsequently, it is stirred at a stirring speed of 4000 r / min - 5000 r / min for 3 h - 4 h to form an emulsion.

[0012] As a further solution of the present invention: in the step five, the intelligent antibacterial slow-release microspheres are added to the quasi-liquid fertilizer according to the proportion of 0.5% - 0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 42 °C - 45 °C, the intelligent antibacterial slow-release microspheres are uniformly dispersed in the liquid fertilizer. Subsequently, it is stirred at a stirring speed of 60 r / min - 80 r / min for 1.0 h - 1.5 h. Then, plant trine is added, and the plant trine is added to the quasi-liquid fertilizer according to the proportion of 1% - 3% of the mass of the quasi-liquid fertilizer. Subsequently, under the conditions of a temperature of 38 °C - 42 °C and a stirring speed of 60 r / min - 80 r / min, a low-speed stirring reaction is carried out for 1.5 h - 2.5 h to obtain the final liquid fertilizer.

[0013] As a further solution of the present invention: in the step five, in the preparation process of the plant tricin, Bacillus subtilis and Bacillus licheniformis are selected for standby. The Triple-MAX triple glycolysis process is as follows: Bacillus subtilis and Bacillus licheniformis are mixed in a volume ratio of 1:1 - 1.3 and then inoculated into the fermentation medium. The fermentation medium contains glucose with a mass fraction of 15% - 25%, peptone with a mass fraction of 8% - 12%, yeast extract with a mass fraction of 3% - 7%, magnesium sulfate with a mass fraction of 0.3% - 0.7%, and potassium dihydrogen phosphate with a mass fraction of 0.2% - 0.4%. Under the conditions of a temperature of 28°C - 32°C and a pH value of 7.0 - 7.4, aerobic fermentation is carried out for 10h - 14h. Subsequently, under the conditions of a temperature of 23°C - 27°C and a pH value of 6.6 - 7.0, anaerobic fermentation is carried out for 6h - 10h. Finally, under the conditions of a temperature of 26°C - 30°C and a pH value of 6.8 - 7.2, micro-aerobic fermentation is carried out for 4h - 8h. The "Multi-Point" enzymatic oligopeptide process is as follows: the fermentation product is separated and purified to obtain a crude extract. A specific protease K enzyme preparation with an enzyme activity of 4000U / mg - 6000U / mg is added to the crude extract, and the addition amount of the enzyme preparation is 1% - 2% of the mass of the crude extract. Under the environment of a temperature of 38°C - 42°C and a pH value of 7.3 - 7.7, the reaction is carried out for 4h - 6h. The "Bio-Synthesis" process is as follows: the product after the enzymatic oligopeptide reaction is transferred to a biosynthesis reactor, and glycine with a purity of 98% - 99.5% and coenzyme NADPH with a purity of 97% - 99% are added. The addition amount of the precursor substance is 2% - 4% of the mass of the reaction system, and the addition amount of the coenzyme is 0.5% - 1.5% of the mass of the reaction system. Under the conditions of a temperature of 35 - 39°C and a pH value of 7.6 - 8.0, the reaction is carried out for 6h - 10h to complete the preparation of the plant tricin.

[0014] Adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows: 1. The present invention uses aniline containing an amino group and acetic acid containing a carboxyl group as starting materials. The two can respectively provide amino and carboxyl functional groups. Under the catalysis of sulfuric acid, an esterification reaction is carried out to construct the basic structural framework of the complexing agent, forming an intermediate with partial coordination ability. Then, mercaptoethanol is introduced to provide a mercapto functional group, and the mercapto group is introduced into the molecular structure through a nucleophilic substitution reaction, so that the finally synthesized complexing agent has multiple different types of coordination sites, including amino, carboxyl, mercapto, etc. These sites can form stable coordination bonds with metal ions (transition metal ions such as iron, zinc, copper, etc.), organic acid root ions and other active components in the ivermectin waste liquid, effectively complexing potential reactive components, reducing their reactivity when mixed with other fertilizers or pesticides, preventing compatibility problems such as precipitation and flocculation. For the prepared compatibility regulator, the hydrophilic group of the non-ionic surfactant is composed of a polyoxyethylene chain segment, which is electrically neutral in solution. Its lipophilic group has good affinity with the organic components in the fertilizer, can reduce the surface tension of the liquid fertilizer, and promote the better dispersion of the fertilizer in the mixed system. The anionic surfactant sodium dodecylbenzenesulfonate is negatively charged and can enhance the electrostatic repulsion between fertilizer particles to prevent their agglomeration. The two complement each other to improve the interfacial properties of the liquid fertilizer mixed system, enabling the fertilizer to be evenly dispersed when mixed with other substances, reducing phenomena such as flocculation and precipitation caused by interface instability, and enhancing chemical stability. After the treated liquid fertilizer is mixed and stored with various fertilizers and pesticides, its physical and chemical properties are stable, and the adverse phenomena are significantly reduced, with extremely strong compatibility, greatly improving the comprehensive application benefits in agricultural production; 2. The present invention synthesizes intelligent antibacterial slow-release microspheres. Ethyl orthosilicate is hydrolyzed and polycondensed by ammonia catalysis to prepare porous silica nanoparticles. After regulating their pore size and particle size, metal ions are loaded, and then a biodegradable poly(lactic-co-glycolic acid) copolymer layer is coated. When added to the liquid fertilizer, during normal storage, the poly(lactic-co-glycolic acid) copolymer layer effectively maintains the stability of the microspheres and prevents the rapid release of metal ions. When microorganisms grow, the acidic substances metabolized by them cause the degradation of the poly(lactic-co-glycolic acid) copolymer layer, releasing metal ions with broad-spectrum antibacterial activity, which can accurately target various microorganisms in the liquid fertilizer, including bacteria, fungi and molds, etc., and strongly inhibit or kill them, thus eliminating the phenomenon of fertilizer spoilage. As the microorganisms are inhibited, the degradation of the poly(lactic-co-glycolic acid) copolymer layer slows down, and the release amount of metal ions is automatically adjusted and reduced, achieving an intelligent controlled release effect. It not only effectively solves the problems of microorganism growth and spoilage, but also can accurately control the release of the antibacterial agent, reducing the waste of the antibacterial agent and its potential impact on the environment, and improving the quality and storage stability of the liquid fertilizer. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic diagram of the process steps in the embodiment of the present invention; Figure 2Schematic diagram of the turbidity parameter for the compatibility test of the examples and comparative examples in the embodiments of the present invention; Figure 3 Schematic diagram of the parameter change of the compatibility components in the examples and comparative examples in the embodiments of the present invention; Figure 4 Schematic diagram of the test parameters for microbial growth and spoilage in the embodiments of the present invention. Detailed implementation manners

[0016] The following further describes the detailed implementation manners of the present invention in conjunction with the drawings. It should be noted here that the description of these implementation manners is used to help understand the present invention, but does not limit the present invention.

[0017] In addition, the technical features involved in the various implementation manners of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0018] Please refer to the attached Figure 1 - attached Figure 4 , a novel process for preparing liquid fertilizer from ivermectin waste liquid of the present invention, the process includes the following specific steps: Step 1. Pretreatment of ivermectin waste liquid: Pour the ivermectin waste liquid into a reaction kettle, then start the stirring device to stir. After stirring is completed, filter and remove impurities with a filter screen. Then adjust the pH value of the waste liquid, and continue to stir after adjustment to complete the pretreatment of the ivermectin waste liquid; Step 2. Select aniline containing amino group and acetic acid containing carboxyl group as starting materials, use sulfuric acid as a catalyst for esterification reaction to form an intermediate with partial coordination ability. Then slowly add the prepared intermediate into a reaction vessel containing mercaptoethanol, and at the same time add a basic catalyst triethylamine for nucleophilic substitution reaction. During the reaction process, use a buffer solution to maintain the pH value of the reaction system, and introduce a mercapto group to obtain a complexing agent; Place the pretreated ivermectin waste liquid in a reaction kettle, slowly add the prepared complexing agent to the waste liquid, then start the stirring device at a low speed for stirring at room temperature. After stirring for a period of time, gradually increase the stirring speed, and then increase the temperature of the reaction kettle for reaction to obtain a semi-finished liquid fertilizer; Step 3. Prepare a compatibility regulator: Mix the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate, then add a buffer to the mixture, and then place the mixed system in a high-speed stirrer for stirring reaction at room temperature to obtain a compatibility regulator. Then slowly add the compatibility regulator to the semi-finished liquid fertilizer, and use a high-shear homogenizer to homogenize the mixed system after adding to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator; Step 4: Using tetraethyl orthosilicate as the silicon source, hydrolyze and polycondense it in an ethanol-water mixed solution under the catalysis of ammonia water, stir and react to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a silver nitrate solution, and stir and react at room temperature to obtain silver ion-loaded nanoparticles. Subsequently, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) on the surface of the silver ion-loaded nanoparticles as a sustained-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a dichloromethane solution of poly(lactic-co-glycolic acid), then drop it into an aqueous phase containing polyvinyl alcohol, and then stir and react to form an emulsion to obtain intelligent antibacterial sustained-release microspheres; Step 5: The plant triterpenoids are prepared by the three major processes of Triple-MAX triple glycolysis, "Multi-Point" enzymatic oligopeptides, and "Bio-Synthesis biosynthesis". Add the prepared intelligent antibacterial sustained-release microspheres and plant triterpenoids to the quasi-liquid fertilizer, and then carry out low-speed stirring reaction to obtain the final liquid fertilizer.

[0019] In one embodiment of the present invention: In Step 1, pour the ivermectin waste liquid into the reaction kettle, then turn on the stirring device, stir at a stirring speed of 100 r / min - 150 r / min for 30 min - 45 min, then filter and remove impurities using a filter screen with a pore size of 80 μm - 100 μm, and then use 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution to adjust the pH value to 7.0 - 8.0. After the adjustment is completed, continue to stir for 15 min - 20 min.

[0020] In one embodiment of the present invention: In Step 2, the molar ratio of the starting materials aniline and acetic acid is 1:1.2 - 1.3, the concentration of the catalyst sulfuric acid is 98% - 99%, carry out the esterification reaction at 80°C - 100°C for 4 h - 6 h, the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:1.5 - 2, and the molar ratio of the added triethylamine to the intermediate is 0.1 - 0.2:1. Then control the temperature at 60°C - 80°C to carry out the nucleophilic substitution reaction between the intermediate and mercaptoethanol, control the reaction time to be 3 h - 5 h. During the reaction process, use a potassium dihydrogen phosphate-disodium hydrogen phosphate buffer solution to maintain the pH value of the reaction system at 6 - 7.

[0021] In one embodiment of the present invention: In step two, the addition amount of the complexing agent is 2% - 3% of the mass of the waste liquid. Subsequently, the stirring device is turned on at room temperature, the stirring speed is initially set at 80 r / min - 100 r / min, and after continuously stirring for 20 min - 30 min, the stirring speed is gradually increased to 300 r / min - 350 r / min, and the temperature of the reaction kettle is raised to 50°C - 55°C. Under these conditions, the reaction proceeds for 2 h - 3 h. During the reaction process, the concentration change of the active ingredient in the waste liquid is monitored in real time by an on-line ultraviolet-visible spectrometer. When the concentration of the active ingredient is monitored to decrease to less than 10% of the initial concentration, the reaction is stopped.

[0022] In one embodiment of the present invention: In step three, polyoxyethylene sorbitan fatty acid ester and sodium dodecylbenzenesulfonate are mixed in a mass ratio of 2.5 - 3:1, and the buffer is selected as the potassium dihydrogen phosphate-disodium hydrogen phosphate buffer system and mixed in a ratio adjusted to a pH value of 6.5 - 7.5. The stirring speed of the high-speed stirrer is 1500 r / min - 2000 r / min, and the stirring time is 45 min - 60 min to obtain a compatibility regulator.

[0023] In one embodiment of the present invention: In step three, the addition amount of the compatibility regulator is 2.0% - 2.5% of the total mass of the liquid fertilizer semi-finished product, the rotation speed of the homogenizer is set at 4000 r / min - 5000 r / min, and the homogenization time is 8 min - 10 min.

[0024] In one embodiment of the present invention: In step four, the concentration of ammonia water is 25% - 28%, and the molar ratio of tetraethyl orthosilicate, ethanol, water, and ammonia water is 0.7 - 1:4:2:0.1. The reaction is stirred at 30°C - 33°C for 3 h - 4 h to form silicon dioxide nanoparticles.

[0025] In one embodiment of the present invention: In step four, the prepared silicon dioxide nanoparticles are immersed in a silver nitrate solution with a concentration of 0.1 mol / L - 0.2 mol / L and stirred at room temperature for 18 h - 20 h to obtain silver ion-loaded nanoparticles. The concentration of poly(lactic-co-glycolic acid) in the dichloromethane solution is 10% - 15%, and the concentration of polyvinyl alcohol in the aqueous phase is 2% - 3%. Subsequently, it is stirred at a stirring speed of 4000 r / min - 5000 r / min for 3 h - 4 h to form an emulsion.

[0026] In one embodiment of the present invention: In step five, the intelligent antibacterial sustained-release microspheres are added to the quasi-liquid fertilizer at a ratio of 0.5%-0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 42°C - 45°C, the intelligent antibacterial sustained-release microspheres are uniformly dispersed into the liquid fertilizer, and then stirred at a stirring speed of 60r / min - 80r / min for 1.0h - 1.5h. Subsequently, the plant trinity is added. The plant trinity is added to the quasi-liquid fertilizer at a ratio of 1%-3% of the mass of the quasi-liquid fertilizer. Then, under the conditions of a temperature of 38°C - 42°C and a stirring speed of 60r / min - 80r / min, a low-speed stirring reaction is carried out for 1.5h - 2.5h to obtain the final liquid fertilizer.

[0027] In one embodiment of the present invention: In the preparation process of the plant trinity in step five, Bacillus subtilis and Bacillus licheniformis are selected and reserved. The Triple-MAX triple glycolysis process is as follows: Bacillus subtilis and Bacillus licheniformis are mixed at a volume ratio of 1:1 - 1.3 and then inoculated into the fermentation medium. The fermentation medium contains 15%-25% glucose, 8%-12% peptone, 3%-7% yeast extract, 0.3%-0.7% magnesium sulfate, and 0.2%-0.4% potassium dihydrogen phosphate by mass fraction. Under the conditions of a temperature of 28°C - 32°C and a pH value of 7.0 - 7.4, aerobic fermentation is carried out for 10h - 14h. Subsequently, under the conditions of a temperature of 23°C - 27°C and a pH value of 6.6 - 7.0, anaerobic fermentation is carried out for 6h - 10h. Finally, under the conditions of a temperature of 26°C - 30°C and a pH value of 6.8 - 7.2, microaerobic fermentation is carried out for 4h - 8h. The "Multi-Point" enzymatic oligopeptide process is as follows: The fermentation product is separated and purified to obtain a crude extract. A specific protease K enzyme preparation with an enzyme activity of 4000U / mg - 6000U / mg is added to the crude extract, and the addition amount of the enzyme preparation is 1%-2% of the mass of the crude extract. Under the environment of a temperature of 38°C - 42°C and a pH value of 7.3 - 7.7, the reaction is carried out for 4h - 6h. The "Bio-Synthesis biosynthesis" process is as follows: The product after the enzymatic oligopeptide reaction is transferred to a biosynthesis reactor, and glycine with a purity of 98%-99.5% and coenzyme NADPH with a purity of 97%-99% are added. The addition amount of the precursor substance is 2%-4% of the mass of the reaction system, and the addition amount of the coenzyme is 0.5%-1.5% of the mass of the reaction system. Under the conditions of a temperature of 35 - 39°C and a pH value of 7.6 - 8.0, the reaction is carried out for 6h - 10h to complete the preparation of the plant trinity.

[0028] In one embodiment of the present invention: in step two, during the synthesis of the complexing agent, after the nucleophilic substitution reaction is completed, unreacted mercaptoethanol and low-boiling solvents are first removed by vacuum distillation, and then the residue is separated and purified by silica gel column chromatography. Using a petroleum ether-ethyl acetate mixed solvent (volume ratio 5-10:1) as the eluent, the eluate containing the target complexing agent is collected and concentrated under reduced pressure to obtain a high-purity complexing agent. This high-purity complexing agent can complex with the active ingredients in the waste liquid more precisely and efficiently, improving the complexing effect and the stability of the subsequent liquid fertilizer.

[0029] In one embodiment of the present invention: in step four, before coating the silver ion-loaded nanoparticles with poly(lactic-co-glycolic acid), the surface of the nanoparticles is first modified with a silane coupling agent. The silane coupling agent is γ-aminopropyltriethoxysilane. The silver ion-loaded nanoparticles are immersed in an ethanol solution with a silane coupling agent concentration of 1%-3% and stirred at 40-50 °C for 2h-4h, and then washed and dried with ethanol. After this modification, the binding force between the nanoparticles and the coating layer of poly(lactic-co-glycolic acid) is stronger, which can effectively reduce the risk of the coating layer peeling off during storage and use, thereby more stably controlling the release of metal ions and enhancing the persistence of the antibacterial effect.

[0030] In one embodiment of the present invention: in step five, after the intelligent antibacterial slow-release microspheres are added to the quasi-liquid fertilizer, it further includes a step of performing ultrasonic-microwave synergistic treatment on the mixed system. Under the conditions of an ultrasonic power of 300-500W and a microwave power of 400-600W, it is treated for 10min-20min, so that the intelligent antibacterial slow-release microspheres are more uniformly dispersed in the liquid fertilizer and fully integrated with the liquid fertilizer system, further improving the antibacterial stability and uniformity of the liquid fertilizer, and reducing the problems of local antibacterial effect differences and uneven nutrient distribution caused by microsphere aggregation.

[0031] Example 1. Please refer to the attached Figure 1 - attached Figure 4, introduce the ivermectin waste liquid into the pretreatment reaction kettle, start the stirring device, stir at a stirring speed of 150 r / min for 45 min, filter out impurity particles using a 100-μm filter screen, adjust the pH value to 8.0 using 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution, continue stirring for 20 min after adjustment. Select aniline containing amino group and acetic acid containing carboxyl group as starting materials, where the molar ratio of aniline to acetic acid is 1:1.3, use sulfuric acid with a concentration of 99% as a catalyst, carry out an esterification reaction at 100 °C for 6 h to form an intermediate with partial coordination ability. Slowly add the intermediate to a reaction vessel containing mercaptoethanol, and the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:2. At the same time, add the alkaline catalyst triethylamine, and the molar ratio of triethylamine to the intermediate is 0.2:1. Control the temperature at 80 °C to carry out a nucleophilic substitution reaction between the intermediate and mercaptoethanol for 5 h, and use potassium dihydrogen phosphate-disodium hydrogen phosphate buffer solution to maintain the pH value of the reaction system at 7. Place the pretreated ivermectin waste liquid in the reaction kettle, slowly add the prepared complexing agent to the waste liquid, and the addition amount of the complexing agent is 3% of the mass of the waste liquid. Start the stirring device at room temperature, initially set the stirring speed to 100 r / min, gradually increase the stirring speed to 350 r / min after continuously stirring for 30 min, and raise the temperature of the reaction kettle to 55 °C. React under these conditions for 3 h, and monitor the change in the concentration of the active ingredient in the waste liquid in real time through an on-line ultraviolet-visible spectrometer. When it is monitored that the concentration of the active ingredient decreases to less than 10% of the initial concentration, stop the reaction to obtain a semi-finished liquid fertilizer. Prepare a compatibility regulator by mixing the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate according to a mass ratio of 3:1, add a buffer, and select the potassium dihydrogen phosphate-disodium hydrogen phosphate buffer system as the buffer, and mix according to the ratio adjusted to a pH value of 7.5. Place the mixed system in a high-speed stirrer at room temperature for mixing, with a stirring speed of 2000 r / min and a stirring time of 60 min to obtain a compatibility regulator. Slowly add the compatibility regulator to the semi-finished liquid fertilizer, and the addition amount of the compatibility regulator is 2.5% of the total mass of the semi-finished liquid fertilizer. Use a high-shear homogenizer to homogenize the mixed system, set the rotation speed of the homogenizer to 5000 r / min, and the homogenization time to 10 min to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator. Use tetraethyl orthosilicate as the silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of ammonia water with a concentration of 28%, and the molar ratio of tetraethyl orthosilicate, ethanol, water and ammonia water is 1:4:2:0.1. React with stirring at 33 °C for 4 h to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a concentration of 0.In a 2 mol / L silver nitrate solution, stir at room temperature for 20 h to fully load silver ions into the pores of the nanoparticles, obtaining silver ion-loaded nanoparticles. Then, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) on the surface of the silver ion-loaded nanoparticles as a sustained-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a 15% poly(lactic-co-glycolic acid) dichloromethane solution, and then drop it into an aqueous phase containing 3% polyvinyl alcohol. Stir at a speed of 5000 r / min for 4 h to form an emulsion, and let the organic solvent evaporate. Poly(lactic-co-glycolic acid) forms a coating layer on the surface of the nanoparticles, obtaining intelligent antibacterial sustained-release microspheres. Add the prepared intelligent antibacterial sustained-release microspheres to the quasi-liquid fertilizer at a ratio of 0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 45 °C, disperse the intelligent antibacterial sustained-release microspheres evenly in the liquid fertilizer, stir at a speed of 80 r / min for 1.5 h, and then prepare plant tricin. Select Bacillus subtilis and Bacillus licheniformis for standby. The Triple-MAX triple glycolysis process is as follows: Mix Bacillus subtilis and Bacillus licheniformis at a volume ratio of 1:1.3 and inoculate them into the fermentation medium. The fermentation medium contains 25% glucose, 12% peptone, 7% yeast extract, 0.7% magnesium sulfate, and 0.4% potassium dihydrogen phosphate by mass fraction. Under the conditions of a temperature of 32 °C and a pH value of 7.4, carry out aerobic fermentation for 14 h. Subsequently, under the conditions of a temperature of 27 °C and a pH value of 7.0, carry out anaerobic fermentation for 10 h. Finally, under the conditions of a temperature of 30 °C and a pH value of 7.2, carry out microaerobic fermentation for 8 h. The "Multi-Point" enzymatic oligopeptide process is as follows: Separate and purify the fermentation product to obtain a crude extract. Add a specific protease K enzyme preparation with an enzyme activity of 6000 U / mg to the crude extract, and the addition amount of the enzyme preparation is 2% of the mass of the crude extract. React at a temperature of 42 °C and a pH value of 7.7 for 6 h. The "Bio-Synthesis biosynthesis" process is as follows: Transfer the product after the enzymatic oligopeptide reaction to a biosynthesis reactor, add precursor glycine with a purity of 99.5% and coenzyme NADPH with a purity of 99%. The addition amount of the precursor is 4% of the mass of the reaction system, and the addition amount of the coenzyme is 1.5% of the mass of the reaction system. React under the conditions of a temperature of 39 °C and a pH value of 8.0 for 10 h to complete the preparation of plant tricin. Subsequently, add plant tricin to the quasi-liquid fertilizer. The plant tricin is added to the quasi-liquid fertilizer at a ratio of 3% of the mass of the quasi-liquid fertilizer. Then, carry out a low-speed stirring reaction at a temperature of 42 °C and a stirring speed of 80 r / min for 2.5 h to obtain the final liquid fertilizer.

[0032] Example 2. Please refer to the attached Figure 1 - attached Figure 4, introduce the ivermectin waste liquid into the pretreatment reaction kettle, start the stirring device, stir at a stirring speed of 100 r / min for 30 min, filter to remove impurity particles using an 80-μm filter screen, use 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution to adjust the pH value to 7.0, continue stirring for 15 min after the adjustment is completed. Select aniline containing amino group and acetic acid containing carboxyl group as starting materials, where the molar ratio of aniline to acetic acid is 1:1.2. Use sulfuric acid with a concentration of 98% as a catalyst, and carry out an esterification reaction at 80 °C for 4 h to form an intermediate with partial coordination ability. Slowly add the intermediate to the reaction vessel containing mercaptoethanol, and the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:1.5. At the same time, add the alkaline catalyst triethylamine, and the molar ratio of triethylamine to the intermediate is 0.1:1. Control the temperature at 60 °C to carry out a nucleophilic substitution reaction between the intermediate and mercaptoethanol for 3 h. Use potassium dihydrogen phosphate-disodium hydrogen phosphate buffer solution to maintain the pH value of the reaction system at 6. Place the pretreated ivermectin waste liquid in the reaction kettle, slowly add the prepared complexing agent to the waste liquid, and the addition amount of the complexing agent is 2% of the mass of the waste liquid. Start the stirring device at room temperature, initially set the stirring speed at 80 r / min, after continuously stirring for 20 min, gradually increase the stirring speed to 300 r / min, and raise the temperature of the reaction kettle to 50 °C. React under these conditions for 2 h, and monitor the change in the concentration of the active ingredient in the waste liquid in real time through an on-line ultraviolet-visible spectrometer. When it is monitored that the concentration of the active ingredient decreases to less than 20% of the initial concentration, stop the reaction to obtain a semi-finished liquid fertilizer. Prepare a compatibility regulator. Mix the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate according to a mass ratio of 2.5:1, add a buffer, and select the potassium dihydrogen phosphate-disodium hydrogen phosphate buffer system as the buffer. Mix according to the ratio adjusted to a pH value of 6.5. Place the mixed system in a high-speed stirrer at room temperature for mixing, with a stirring speed of 1500 r / min and a stirring time of 45 min to obtain a compatibility regulator. Slowly add the compatibility regulator to the semi-finished liquid fertilizer, and the addition amount of the compatibility regulator is 2.0% of the total mass of the semi-finished liquid fertilizer. Use a high-shear homogenizer to homogenize the mixed system, set the rotation speed of the homogenizer at 4000 r / min, and the homogenization time at 8 min to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator. Use tetraethyl orthosilicate as a silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of ammonia water with a concentration of 25%. The molar ratio of tetraethyl orthosilicate, ethanol, water, and ammonia water is 0.7:4:2:0.1. The reaction is stirred at 30 °C for 3 h to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a concentration of 0.In a 1 mol / L silver nitrate solution, stir at room temperature for 18 h to fully load silver ions into the pores of the nanoparticles, obtaining silver ion-loaded nanoparticles. Then, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) copolymer on the surface of the silver ion-loaded nanoparticles as a sustained-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a 10% poly(lactic-co-glycolic acid) dichloromethane solution, and then drop it into an aqueous phase containing 2% polyvinyl alcohol. Stir at a speed of 4000 r / min for 3 h to form an emulsion, and let the organic solvent evaporate. The poly(lactic-co-glycolic acid) copolymer forms a coating layer on the surface of the nanoparticles, obtaining intelligent antibacterial sustained-release microspheres. Add the prepared intelligent antibacterial sustained-release microspheres to the quasi-liquid fertilizer according to a ratio of 0.5% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 42 °C, disperse the intelligent antibacterial sustained-release microspheres evenly in the liquid fertilizer, stir at a speed of 80 r / min for 1.5 h, and then prepare plant tricin. Select Bacillus subtilis and Bacillus licheniformis for standby. The Triple-MAX triple glycolysis process is as follows: Mix Bacillus subtilis and Bacillus licheniformis according to a volume ratio of 1:1 and inoculate them into the fermentation medium. The fermentation medium contains 15% glucose, 8% peptone, 3% yeast extract, 0.3% magnesium sulfate, and 0.2% potassium dihydrogen phosphate by mass fraction. Under the conditions of a temperature of 28 °C and a pH value of 7.0, carry out aerobic fermentation for 10 h. Subsequently, under the conditions of a temperature of 23 °C and a pH value of 6.6, carry out anaerobic fermentation for 6 h. Finally, under the conditions of a temperature of 26 °C and a pH value of 6.8, carry out microaerobic fermentation for 4 h. The "Multi-Point" enzymatic oligopeptide process is as follows: Separate and purify the fermentation product to obtain a crude extract. Add a specific protease K enzyme preparation with an enzyme activity of 4000 U / mg to the crude extract, and the addition amount of the enzyme preparation is 1% of the mass of the crude extract. React at a temperature of 38 °C and a pH value of 7.3 for 4 h. The "Bio-Synthesis biosynthesis" process is as follows: Transfer the product after the enzymatic oligopeptide reaction to a biosynthesis reactor, add precursor glycine with a purity of 98% and coenzyme NADPH with a purity of 97%. The addition amount of the precursor is 2% of the mass of the reaction system, and the addition amount of the coenzyme is 0.5% of the mass of the reaction system. React at a temperature of 35 °C and a pH value of 7.6 for 6 h to complete the preparation of plant tricin. Subsequently, add plant tricin to the quasi-liquid fertilizer. The plant tricin is added to the quasi-liquid fertilizer according to a ratio of 1% of the mass of the quasi-liquid fertilizer. Then, carry out a low-speed stirring reaction at a temperature of 38 °C and a stirring speed of 60 r / min for 1.5 h to obtain the final liquid fertilizer. Comparative Example 1. Please refer to Appendix Figure 1 - Appendix Figure 4, introduce the ivermectin waste liquid into the pretreatment reactor, start the stirring device, stir at a stirring speed of 150 r / min for 45 min, filter out impurity particles using a 100-μm filter screen, adjust the pH value to 8.0 using 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution, continue stirring for 20 min after adjustment. Select phenethylamine containing an amino group and acetic acid containing a carboxyl group as starting materials, where the molar ratio of phenethylamine to acetic acid is 1:1.3. Use sulfuric acid with a concentration of 99% as a catalyst, and carry out an esterification reaction at 100 °C for 6 h to form an intermediate with partial coordination ability. Slowly add the intermediate to a reaction vessel containing mercaptoethanol, and the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:2. At the same time, add the basic catalyst triethylamine, and the molar ratio of triethylamine to the intermediate is 0.2:1. Control the temperature at 80 °C to carry out a nucleophilic substitution reaction between the intermediate and mercaptoethanol for 5 h, and use a potassium dihydrogen phosphate-disodium hydrogen phosphate buffer solution to maintain the pH value of the reaction system at 7. Place the pretreated ivermectin waste liquid in the reactor, slowly add the prepared complexing agent to the waste liquid, and the addition amount of the complexing agent is 3% of the mass of the waste liquid. Start the stirring device at room temperature, initially set the stirring speed to 100 r / min, after continuously stirring for 30 min, gradually increase the stirring speed to 350 r / min, and raise the temperature of the reactor to 55 °C. React under these conditions for 3 h, and monitor the change in the concentration of the active ingredient in the waste liquid in real time through an online ultraviolet-visible spectrometer. When the monitored concentration of the active ingredient decreases to less than 10% of the initial concentration, stop the reaction to obtain a semi-finished liquid fertilizer. Prepare a compatibility regulator by mixing the non-ionic surfactant polyoxyethylene alkyl ether and the anionic surfactant sodium dodecyl sulfate according to a mass ratio of 3:1, add a buffer, and select a potassium dihydrogen phosphate-disodium hydrogen phosphate buffer system as the buffer. Mix according to the ratio adjusted to a pH value of 7.5, place the mixed system in a high-speed stirrer at room temperature for mixing, with a stirring speed of 2000 r / min and a stirring time of 60 min to obtain a compatibility regulator. Slowly add the compatibility regulator to the semi-finished liquid fertilizer, and the addition amount of the compatibility regulator is 2.5% of the total mass of the semi-finished liquid fertilizer. Use a high-shear homogenizer to homogenize the mixed system, set the rotation speed of the homogenizer to 5000 r / min, and the homogenization time to 10 min to obtain a quasi-liquid fertilizer with the compatibility regulator uniformly dispersed. Use tetraethyl orthosilicate as a silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of 28% ammonia water, and the molar ratio of tetraethyl orthosilicate, ethanol, water, and ammonia water is 1:4:2:0.1. The reaction is stirred at 33 °C for 4 h to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a concentration of 0.In a 2 mol / L silver nitrate solution, stir at room temperature for 20 h to fully load silver ions into the pores of the nanoparticles, obtaining silver ion-loaded nanoparticles. Then, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) on the surface of the silver ion-loaded nanoparticles as a slow-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a 15% poly(lactic-co-glycolic acid) dichloromethane solution, and then drop it into an aqueous phase containing 3% polyvinyl alcohol. Stir at a speed of 5000 r / min for 4 h to form an emulsion. Let the organic solvent evaporate, and poly(lactic-co-glycolic acid) forms a coating layer on the surface of the nanoparticles, obtaining intelligent antibacterial slow-release microspheres. Add the prepared intelligent antibacterial slow-release microspheres to the quasi-liquid fertilizer according to a ratio of 0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 45 °C, disperse the intelligent antibacterial slow-release microspheres evenly in the liquid fertilizer and stir at a speed of 80 r / min for 1.5 h to obtain the final liquid fertilizer.

[0033] Comparative Example 2. Please refer to the appendix Figure 1 - Appendix Figure 4, introduce the ivermectin waste liquid into the pretreatment reactor, start the stirring device, stir at a stirring speed of 150 r / min for 45 min, filter out impurity particles using a 200-μm filter screen, adjust the pH value to 8.0 using 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution, continue stirring for 20 min after adjustment. Select aniline containing amino group and acetic acid containing carboxyl group as starting materials, where the molar ratio of aniline to acetic acid is 1:1.5, use sulfuric acid with a concentration of 99% as a catalyst, carry out an esterification reaction at 100 °C for 6 h to form an intermediate with partial coordination ability. Slowly add the intermediate to a reaction vessel containing mercaptoethanol, and the molar ratio of the intermediate to mercaptoethanol in the mixture is 1:2. At the same time, add the basic catalyst triethylamine, and the molar ratio of triethylamine to the intermediate is 0.2:1. Control the temperature at 80 °C to carry out a nucleophilic substitution reaction between the intermediate and mercaptoethanol for 5 h, and use potassium dihydrogen phosphate-disodium hydrogen phosphate buffer solution to maintain the pH value of the reaction system at 7. Place the pretreated ivermectin waste liquid in the reactor, slowly add the prepared complexing agent to the waste liquid, and the addition amount of the complexing agent is 3% of the waste liquid mass. Start the stirring device at room temperature, initially set the stirring speed to 100 r / min, after continuously stirring for 30 min, gradually increase the stirring speed to 350 r / min, and raise the temperature of the reactor to 55 °C. React under these conditions for 3 h, and monitor the concentration change of the active ingredient in the waste liquid in real time through an on-line ultraviolet-visible spectrometer. When it is monitored that the concentration of the active ingredient decreases to less than 10% of the initial concentration, stop the reaction to obtain a semi-finished liquid fertilizer. Prepare a compatibility regulator by mixing the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate in a mass ratio of 3:2, add a buffer, and select the potassium dihydrogen phosphate-disodium hydrogen phosphate buffer system as the buffer, and mix according to the ratio adjusted to a pH value of 7.0. Place the mixed system in a high-speed stirrer at room temperature for mixing, with a stirring speed of 2000 r / min and a stirring time of 60 min to obtain a compatibility regulator. Slowly add the compatibility regulator to the semi-finished liquid fertilizer, and the addition amount of the compatibility regulator is 2.5% of the total mass of the semi-finished liquid fertilizer. Use a high-shear homogenizer to homogenize the mixed system, set the rotation speed of the homogenizer to 5000 r / min, and the homogenization time to 10 min to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator. Use tetraethyl orthosilicate as a silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of 28% ammonia water. The molar ratio of tetraethyl orthosilicate, ethanol, water, and ammonia water is 1:4:3:0.3, and the reaction is stirred at 33 °C for 4 h to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a concentration of 0.In a 2 mol / L silver nitrate solution, stir at room temperature for 20 h to fully load silver ions into the pores of the nanoparticles, obtaining silver ion-loaded nanoparticles. Then, use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) copolymer on the surface of the silver ion-loaded nanoparticles as a sustained-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a 15% poly(lactic-co-glycolic acid) dichloromethane solution, and then drop it into an aqueous phase containing 3% polyvinyl alcohol. Stir at a speed of 5000 r / min for 4 h to form an emulsion. Let the organic solvent evaporate, and the poly(lactic-co-glycolic acid) copolymer forms a coating layer on the surface of the nanoparticles, obtaining intelligent antibacterial sustained-release microspheres. Add the prepared intelligent antibacterial sustained-release microspheres to the quasi-liquid fertilizer at a ratio of 0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 45 °C, disperse the intelligent antibacterial sustained-release microspheres evenly in the liquid fertilizer and stir at a speed of 80 r / min for 1.5 h to obtain the final liquid fertilizer.

[0034] Experimental design Materials: Liquid fertilizer samples prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, chicken manure organic fertilizer, zinc sulfate trace element fertilizer, abamectin insecticide, carbendazim fungicide, glyphosate herbicide, microbial strains such as Escherichia coli, Penicillium, and Aspergillus, culture media such as nutrient agar medium and potato dextrose agar medium; Equipment: Constant temperature incubator, light incubator, electronic balance, pH meter, conductivity meter, microscope, turbidimeter, gas chromatograph, high performance liquid chromatograph, etc.; (I)Compatibility test Respectively take 100 mL of the liquid fertilizers prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 and place them in 250 mL conical flasks; Add 20 g of chicken manure organic fertilizer, 5 g of zinc sulfate trace element fertilizer, 5 mL of abamectin insecticide, 5 mL of carbendazim fungicide, and 5 mL of glyphosate herbicide to each conical flask in sequence. At room temperature (25 °C ± 2 °C), use a magnetic stirrer to stir at a speed of 200 r / min for 30 min to fully mix the fertilizer and pesticides; Transfer the mixed solutions to 100 mL measuring cylinders respectively, let them stand and observe for 7 days, record whether there are precipitation and flocculation phenomena, and use a turbidimeter to measure the initial turbidity of the solution and the turbidity change after standing for 7 days. The specific data are shown in the appendix Figure 2 ; Take the mixed solution and use a high performance liquid chromatograph and a gas chromatograph to detect the content changes of the active ingredients (such as abamectin, carbendazim, glyphosate, etc.) respectively to evaluate the chemical stability after mixing with pesticides. The data are shown in the appendix Figure 3 as shown; (II)Microbial growth and spoilage test Preparation of microbial suspensions: Microbial strains such as Escherichia coli, Penicillium, and Aspergillus were inoculated into the corresponding liquid media and cultured at 30 °C for 24 - 48 h until the microorganisms grew to the logarithmic phase. Then, the bacterial solutions were diluted with sterile normal saline to a concentration of 1×10^6 - 1×10^7 CFU / mL. Take 50 mL of the liquid fertilizers prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 respectively, place them in 100 mL Erlenmeyer flasks, and add 5 mL of the above microbial suspensions to each Erlenmeyer flask, and shake well. Place the liquid fertilizer samples inoculated with microorganisms in an incubator and culture at 28 °C for 14 days. Every two days, take out the samples, measure the pH value change of the solution using a pH meter, measure the conductivity change using a conductivity meter, observe the changes in the odor, color, and transparency of the solution, and take a small amount of the solution to observe the microbial growth under a microscope. After the culture is completed, the plate counting method is used to determine the number of microorganisms in the liquid fertilizer to evaluate the inhibitory effect of different samples on microbial growth. The specific data are as shown in the appendix Figure 4 as follows.

[0035] Through the above experimental steps and parameter settings, a comprehensive test and analysis are carried out on Example 1, Example 2, Comparative Example 1, and Comparative Example 2, and various experimental data are compared to prove the superiority of Example 1 in solving the problems of poor compatibility and microbial growth, spoilage, and deterioration.

[0036] Although the present invention is disclosed above in a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make possible changes and modifications without departing from the spirit and scope of the present invention. Therefore, any modification, equivalent change, and modification made to the above embodiment based on the technical essence of the present invention without departing from the technical solution of the present invention shall fall within the protection scope defined by the claims of the present invention.

Claims

1. A novel process for preparing liquid fertilizer from ivermectin waste liquid, characterized in that, The process includes the following specific steps: Step 1. Pretreatment of ivermectin waste liquid: Pour the ivermectin waste liquid into a reaction kettle, then start the stirring device to stir. After stirring is completed, filter to remove impurities using a filter screen. Then adjust the pH value of the waste liquid, and continue stirring after adjustment to complete the pretreatment of the ivermectin waste liquid; Step 2. Select aniline containing an amino group and acetic acid containing a carboxyl group as starting materials, and use sulfuric acid as a catalyst for an esterification reaction to form an intermediate with partial coordination ability. Then slowly add the prepared intermediate to a reaction vessel containing mercaptoethanol, and at the same time add a basic catalyst, triethylamine, for a nucleophilic substitution reaction. During the reaction, use a buffer solution to maintain the pH value of the reaction system, and introduce a mercapto group in the reaction to obtain a complexing agent; Place the pretreated ivermectin waste liquid in a reaction kettle, slowly add the prepared complexing agent to the waste liquid, then start the stirring device at room temperature for low-speed stirring. After stirring for a period of time, gradually increase the stirring speed, and then increase the temperature of the reaction kettle for reaction to obtain a semi-finished liquid fertilizer; Step 3. Prepare a compatibility regulator: Mix the non-ionic surfactant polyoxyethylene sorbitan fatty acid ester and the anionic surfactant sodium dodecylbenzenesulfonate, then add a buffer to the mixture. Then place the mixed system in a high-speed stirrer at room temperature for a stirring reaction to obtain a compatibility regulator. Then slowly add the compatibility regulator to the semi-finished liquid fertilizer, and use a high-shear homogenizer to homogenize the mixed system after addition to obtain a quasi-liquid fertilizer with uniform dispersion of the compatibility regulator; Step 4. Use tetraethyl orthosilicate as a silicon source, hydrolyze and polycondense in an ethanol-water mixed solution under the catalysis of ammonia water, and stir to react to form silicon dioxide nanoparticles. Immerse the prepared silicon dioxide nanoparticles in a silver nitrate solution, and stir to react at room temperature to obtain silver ion-loaded nanoparticles. Then use the emulsion-solvent evaporation method to coat a layer of poly(lactic-co-glycolic acid) on the surface of the silver ion-loaded nanoparticles as a slow-release layer and an intelligent controlled-release switch. Disperse the silver ion-loaded nanoparticles in a dichloromethane solution of poly(lactic-co-glycolic acid), then drop it into an aqueous phase containing polyvinyl alcohol, and then stir to react to form an emulsion to obtain intelligent antibacterial slow-release microspheres; Step 5. Plant triterpenoids are prepared by three major processes: Triple-MAX triple glycolysis, "Multi-Point" enzymatic oligopeptides, and "Bio-Synthesis" biosynthesis. Add the prepared intelligent antibacterial slow-release microspheres and plant triterpenoids to the quasi-liquid fertilizer, and then carry out a low-speed stirring reaction to obtain the final liquid fertilizer.

2. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the said Step 1, after pouring the ivermectin waste liquid into the reaction kettle, start the stirring device, stir at a stirring speed of 100 r / min - 150 r / min for 30 min - 45 min, then filter to remove impurities using a filter screen with a pore size of 80 μm - 100 μm. Then use 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide solution to adjust the pH value to 7.0 - 8.

0. After adjustment, continue stirring for 15 min - 20 min.

3. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the second step, the molar ratio of the starting materials aniline and acetic acid is 1:1.2 - 1.3, the concentration of the catalyst sulfuric acid is 98% - 99%, the esterification reaction is carried out at 80°C - 100°C for 4 h - 6 h, the molar ratio of the intermediate to mercaptoethanol is 1:1.5 - 2, the molar ratio of the added triethylamine to the intermediate is 0.1 - 0.2:1, and then the temperature is controlled at 60°C - 80°C for the intermediate and mercaptoethanol to carry out a nucleophilic substitution reaction, and the reaction time is controlled at 3 h - 5 h. During the reaction process, a potassium dihydrogen phosphate - disodium hydrogen phosphate buffer solution is used to maintain the pH value of the reaction system at 6 - 7.

4. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the second step, the addition amount of the complexing agent is 2% - 3% of the waste liquid mass. Subsequently, the stirring device is started at room temperature, the initial stirring speed is set at 80 r / min - 100 r / min, after continuously stirring for 20 min - 30 min, the stirring speed is gradually increased to 300 r / min - 350 r / min, and the temperature of the reaction kettle is raised to 50°C - 55°C. Under these conditions, the reaction is carried out for 2 h - 3 h. During the reaction process, the concentration change of the active ingredient in the waste liquid is monitored in real time by an on - line ultraviolet - visible spectrometer. When it is monitored that the concentration of the active ingredient is reduced to less than 10% of the initial concentration, the reaction is stopped.

5. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the third step, polyoxyethylene sorbitan fatty acid ester and sodium dodecylbenzenesulfonate are mixed according to a mass ratio of 2.5 - 3:

1. The buffer is selected as a potassium dihydrogen phosphate - disodium hydrogen phosphate buffer system and mixed according to the ratio adjusted to a pH value of 6.5 - 7.

5. The stirring speed of the high - speed stirrer is 1500 r / min - 2000 r / min, and the stirring time is 45 min - 60 min to obtain a compatibility regulator.

6. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the third step, the addition amount of the compatibility regulator is 2.0% - 2.5% of the total mass of the liquid fertilizer semi - product. The rotation speed of the homogenizer is set at 4000 r / min - 5000 r / min, and the homogenization time is 8 min - 10 min.

7. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the fourth step, the concentration of ammonia water is 25% - 28%, the molar ratio of tetraethyl orthosilicate, ethanol, water and ammonia water is 0.7 - 1:4:2:0.1, and the reaction is stirred at 30°C - 33°C for 3 h - 4 h to form silicon dioxide nanoparticles.

8. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the fourth step, the prepared silicon dioxide nanoparticles are soaked in a silver nitrate solution with a concentration of 0.1 mol / L - 0.2 mol / L and stirred at room temperature for 18 h - 20 h to obtain silver - ion - loaded nanoparticles. The concentration of poly(lactic - co - glycolic acid) in dichloromethane solution is 10% - 15%, and the concentration of polyvinyl alcohol in the aqueous phase is 2% - 3%. Subsequently, it is stirred at a stirring speed of 4000 r / min - 5000 r / min for 3 h - 4 h to form an emulsion.

9. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In step 5, the intelligent antibacterial slow-release microspheres are added to the quasi-liquid fertilizer at a ratio of 0.5%-0.7% of the mass of the quasi-liquid fertilizer. When the temperature of the quasi-liquid fertilizer drops to 42°C - 45°C, the intelligent antibacterial slow-release microspheres are evenly dispersed into the liquid fertilizer, and then stirred at a stirring speed of 60 r / min - 80 r / min for 1.0 h - 1.5 h. Subsequently, plant tricin is added. The plant tricin is added to the quasi-liquid fertilizer at a ratio of 1%-3% of the mass of the quasi-liquid fertilizer. Then, under the conditions of a temperature of 38°C - 42°C and a stirring speed of 60 r / min - 80 r / min, a low-speed stirring reaction is carried out for 1.5 h - 2.5 h to obtain the final liquid fertilizer.

10. A novel process for preparing liquid fertilizer from ivermectin waste liquid according to claim 1, characterized in that: In the preparation process of plant tricin in step 5, Bacillus subtilis and Bacillus licheniformis are selected for standby. The Triple-MAX triple glycolysis process is as follows: Bacillus subtilis and Bacillus licheniformis are mixed at a volume ratio of 1:1 - 1.3 and then inoculated into the fermentation medium. The fermentation medium contains 15%-25% glucose, 8%-12% peptone, 3%-7% yeast extract, 0.3%-0.7% magnesium sulfate, and 0.2%-0.4% potassium dihydrogen phosphate by mass fraction. Under the conditions of a temperature of 28°C - 32°C and a pH value of 7.0 - 7.4, aerobic fermentation is carried out for 10 h - 14 h. Subsequently, under the conditions of a temperature of 23°C - 27°C and a pH value of 6.6 - 7.0, anaerobic fermentation is carried out for 6 h - 10 h. Finally, under the conditions of a temperature of 26°C - 30°C and a pH value of 6.8 - 7.2, micro-aerobic fermentation is carried out for 4 h - 8 h. The "Multi-Point" enzymatic oligopeptide process is as follows: The fermentation product is separated and purified to obtain a crude extract. A specific protease K enzyme preparation with an enzyme activity of 4000 U / mg - 6000 U / mg is added to the crude extract, and the addition amount of the enzyme preparation is 1%-2% of the mass of the crude extract. Under the conditions of a temperature of 38°C - 42°C and a pH value of 7.3 - 7.7, the reaction is carried out for 4 h - 6 h. The "Bio-Synthesis" process is as follows: The product after the enzymatic oligopeptide reaction is transferred to a biosynthesis reactor, and precursor glycine with a purity of 98%-99.5% and coenzyme NADPH with a purity of 97%-99% are added. The addition amount of the precursor is 2%-4% of the mass of the reaction system, and the addition amount of the coenzyme is 0.5%-1.5% of the mass of the reaction system. Under the conditions of a temperature of 35 - 39°C and a pH value of 7.6 - 8.0, the reaction is carried out for 6 h - 10 h to complete the preparation of plant tricin.

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