Component optimization method for preparing liquid fertilizer from acetylisovaleryltylosin tartrate waste liquid

Abstract

The invention discloses a component optimization method for preparing a liquid fertilizer from acetylisovaleryltylosin tartrate waste liquid, and relates to the technical field of fertilizer preparation, and the component optimization method comprises the following specific steps: step 1, selecting nanoscale activated carbon with the specific surface area of 1000m < 2 > / g-1500m < 2 > / g as a base material, the method has the advantages that a microbial flora system is constructed by screening out pseudomonas bacteria, actinomycetes and bacillus, and the pseudomonas bacteria can effectively decompose complex organic pollutants in the waste liquid by virtue of the mineralization effect of the pseudomonas bacteria and gradually convert the complex organic pollutants into carbon dioxide, water and simple organic acid, so that the primary purification of the waste liquid is realized; actinomycetes can utilize secreted enzymes to convert acetylisovaleryltylosin tartrate into small molecule compounds containing nitrogen, phosphorus, potassium and other nutrient elements, bacillus further promotes synthesis and stability of the nutrient small molecules, it is ensured that the liquid fertilizer is comprehensive in nutrient and accurate in content, the plant growth requirement can be better met, and the liquid fertilizer has a good application prospect. The resource utilization rate of the acetylisovaleryltylosin tartrate waste liquid is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizer preparation, in particular to a composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid. Background Art

[0002] With the rapid development of animal husbandry and breeding, the production scale of tyvalosin, as a widely used veterinary antibiotic, is continuously expanding. However, a large amount of waste liquid is generated during the production process of tyvalosin. If these waste liquids are not properly treated, they will not only cause waste of resources, but also may cause serious pollution to the environment. At the same time, the demand for efficient and environmentally friendly liquid fertilizers in agricultural production is growing. Therefore, how to effectively treat tyvalosin waste liquid and convert it into valuable liquid fertilizer has become an important issue that needs to be solved urgently. The existing technology has certain defects. The first is that the treatment method of tyvalosin waste liquid is single: the common treatment methods of tyvalosin waste liquid are mostly concentrated on simple physical filtration, chemical neutralization and other conventional means, which have limited removal effect on complex organic pollutants and residual antibiotics in the waste liquid, and cannot fundamentally solve the pollution problem of the waste liquid. Secondly, the stability is insufficient: some liquid fertilizers are prone to stability problems such as precipitation, stratification, and deterioration during storage and use, affecting their fertilizer efficiency and convenience of use. This may be due to the fact that the pH value of the liquid fertilizer, the selection and use of additives are not carefully considered during the preparation process. The other reason is the low resource recovery rate: the existing process focuses on removing harmful substances in the waste liquid to meet the emission standards, but ignores the potential resource value of the waste liquid. For example, some nutrients and organic matter contained therein have not been effectively recovered and reused, resulting in waste of resources. Here, it is necessary to prepare a material to react with the tyvalocin waste liquid, and then extract the tyvalocin in the tyvalocin waste liquid, and then use the extracted high-purity tyvalocin for subsequent preparation of liquid fertilizer. To this end, we propose a composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid. Summary of the invention

[0003] The object of the present invention is to provide a composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid.

[0004] In order to solve the problems raised in the above background technology, the present invention provides the following technical solutions: a composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid, the composition optimization method for preparing liquid fertilizer comprises the following specific steps: Step 1: Select nano-scale activated carbon as a basic material, prepare manganese dioxide nanoparticles for standby use, then prepare a modified cyclodextrin derivative, and then graft the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives onto the surface of the activated carbon by a chemical grafting method to complete the preparation of the multifunctional composite material, and then pre-treat the tyvalosin waste liquid, put the tyvalosin waste liquid and the prepared multifunctional composite material into a reaction container with a stirring device and temperature control for stirring reaction, during which the composite material specifically adsorbs tyvalosin, and at the same time, preliminarily decomposes and adsorbs and removes organic pollutants in the waste liquid; Step 2: After the reaction is completed, the mixed liquid in the reaction container is collected, centrifuged by a centrifuge, eluted with an ethanol solution, the eluate is collected after elution and processed to obtain high-purity tyvalocin, and the waste liquid obtained after centrifugation is filtered, the pH value is adjusted, and then collected for later use; Step 3: construct a microbial flora system of Pseudomonas bacteria, actinomycetes and Bacillus, then connect the treated waste liquid to the microbial flora system for reaction, and after the reaction, centrifuge and collect for later use; Step 4: After the reaction is completed, the microbial cells and the treated waste liquid are separated by centrifugation, and the nutrients are extracted from the separated waste liquid by an ion exchange resin method, and then deionized water is used as a base liquid for preliminary preparation of liquid fertilizer; Step 5: Prepare the nanogel system, add the nanogel system to the preliminary liquid fertilizer solution, add high-purity tyvalocin, and stir and mix thoroughly to form the final liquid fertilizer product. As a further solution of the present invention: in step 1, the base material nano-scale activated carbon with a specific surface area of ​​1000m 2 / g-1500m 2 / g, the prepared manganese dioxide nanoparticles have a particle size of 20nm-50nm and the ratio of cyclodextrin molecules to modifying groups is 1:2, the ratio of cyclodextrin molecules to modifying groups on the surface of manganese dioxide nanoparticles in the prepared modified cyclodextrin derivatives reaches 1:2, and the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives are grafted onto the surface of activated carbon by a chemical grafting method. The specific operation is as follows: under nitrogen protection, the activated carbon is placed in a mixed solution containing cyclodextrin derivatives and manganese dioxide nanoparticles, wherein The concentration of cyclodextrin derivative is 0.3mol / L-0.7mol / L, the concentration of manganese dioxide nanoparticles is 0.2mol / L-0.4mol / L, and then 4%-6% of the mass of activated carbon as coupling agent 3-(trimethoxysilyl)propyl isocyanate is added for stirring reaction, and the reaction is stirred at 45°C-65°C for 20h-28h. After the reaction is completed, the composite material is washed with deionized water and anhydrous ethanol for 3-5 times in turn, and then vacuum dried at 55°C-85°C for 10h-30h.

[0005] As a further solution of the present invention: in the step 1, the tyvalosin waste liquid and the prepared multifunctional composite material are placed in a reaction vessel with a stirring device and temperature control in a volume ratio of 1:3-5, the reaction temperature is set to 30°C-40°C, the stirring speed is 300r / min-500r / min, and the reaction time is 2h-3h.

[0006] As a further scheme of the present invention: in the step 2, the centrifugal speed is set to 4000r / min-6000r / min, the centrifugation time is 10min-20min, and an ethanol solution with a concentration of 60%-80% is used as an eluent. The eluent is eluted at a mass ratio of 4-6:1 between the eluent and the composite material adsorbed with tyvalocin. After elution, the eluate is collected, concentrated under reduced pressure to 1 / 4-1 / 6 of the original volume at 35°C-55°C, and then dried in a vacuum drying oven for 18h-30h, the drying oven temperature is set to 40°C-60°C, and the filtration separation is performed using a filter membrane with a pore size of 0.2μm-0.3μm for filtration and impurity removal, and the pH value is adjusted to 6.0-7.5 with dilute hydrochloric acid and sodium hydroxide solution.

[0007] As a further scheme of the present invention: in the step 3, Pseudomonas bacteria, actinomycetes and Bacillus are screened and inoculated into a culture medium according to a quantitative ratio of 1.5-1.8:1-2.5:3.3, wherein the components of the culture medium include glucose with a concentration of 15g / L-25g / L as a carbon source, ammonium chloride with a concentration of 3g / L-7g / L as a nitrogen source, and a trace element solution containing calcium, magnesium, iron and zinc, and the concentration of each trace element is 0.05g / L-0.15g / L, and the culture is carried out at a temperature of 25°C-35°C and a ventilation volume of 0.3L / min-1.2L / min for 3-5 days, and then the waste liquid treated in step 2 is connected to the reaction container where the cultured microbial flora system is located, and the volume ratio of the waste liquid to the microbial flora is controlled at 1:2-3, and the reaction is stirred at a temperature of 25°C-35°C and a stirring speed of 200r / min-300r / min for 5-7 days.

[0008] As a further scheme of the present invention: in the step 4, the microbial cells and the treated waste liquid are centrifuged at a controlled speed of 3000r / min-5000r / min, the centrifugation time is 15min-25min, and the separated waste liquid is subjected to ion exchange resin method for nutrient extraction. The specific process is as follows: a strongly acidic cation exchange resin and a strongly basic anion exchange resin are mixed in a volume ratio of 0.8-1.2:1, soaked in deionized water and stirred for 2h-4h, repeatedly rinsed 3-5 times until the conductivity is less than 10μS / cm, the mixed resin is loaded into an ion exchange column, and the waste liquid slowly flows through the resin layer at a flow rate of 1mL / min-3mL / min. After the waste liquid has completely flowed through, it is rinsed with deionized water accounting for 10%-20% of the volume of the waste liquid, and 1mol / L-2mol / L hydrochloric acid is used as an eluent, and the nutrients are eluted through the resin at a flow rate of 1mL / min-3mL / min.

[0009] As a further solution of the present invention: in the step 4, the liquid fertilizer is initially prepared with deionized water as the base liquid, ammonium nitrate is added to make the concentration of nitrogen in the base liquid reach 100 mg / L-200 mg / L, potassium dihydrogen phosphate is added to make the concentration of phosphorus in the base liquid 50 mg / L-100 mg / L, potassium nitrate is added to ensure that the concentration of potassium in the base liquid is 150 mg / L-300 mg / L, and composite trace element fertilizers are added to make the concentrations of each trace element in the base liquid respectively: iron element The extract containing high-purity nutrients is added into the base liquid at 100g-150g per liter of deionized water, and urea is added at 3%-7% of the volume of deionized water to supplement nitrogen, and superphosphate is added at 2%-4% of the volume of deionized water to supplement phosphorus.

[0010] As a further solution of the present invention: in the step 5, chitosan is dissolved in a dilute acetic acid solution with a concentration of 0.8%-1.2% to prepare a 2.5% w / v-3.5% w / v chitosan solution, sodium alginate is dissolved in deionized water to prepare a 3.5% w / v-4.5% w / v sodium alginate solution, and the chitosan solution is added dropwise to the sodium alginate solution by an electrostatic drip method and an electric field strength of 600 V / cm-1000 V / cm is applied. , N-isopropylacrylamide (NIPAAm) is grafted onto the surface at a mass ratio of 1:4-6 to the nanogel particles, and acrylic acid (AA) is grafted onto the surface at a mass ratio of 1:5-7 to the nanogel particles. The amount of initiator potassium persulfate is 0.3%-0.7% of the total mass of the monomers. The reaction is carried out at 50℃-70℃ for 2-4h, and then the nanogel system is immersed in an ethanol solution with a concentration of 40%-60% for 18h-30h.

[0011] As a further scheme of the present invention: in the step 5, after obtaining the nanogel system, the prepared nanogel system is finally added to the preliminary liquid fertilizer solution, and the added amount is 3%-7% of the volume of the preliminary liquid fertilizer solution, and the high-purity tyvalocin obtained in step 2 is added to the preliminary liquid fertilizer solution, and the added amount of the high-purity tyvalocin is 5%-8% of the volume of the preliminary liquid fertilizer solution, and the mixture is fully stirred and mixed for 1h-2h at a temperature of 25°C-30°C and a stirring speed of 150r / min-250r / min.

[0012] By adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are: 1. The present invention constructs a microbial flora system by screening out Pseudomonas bacteria, actinomycetes and Bacillus, wherein Pseudomonas bacteria can effectively decompose complex organic pollutants in waste liquid by virtue of its mineralization effect, and gradually convert them into carbon dioxide, water and simple organic acids, thereby achieving preliminary purification of waste liquid and reducing the content of organic pollutants. Actinomycetes can use secreted enzymes to convert tyvalosin into small molecule compounds containing nutrient elements such as nitrogen, phosphorus and potassium, turning waste into treasure and providing effective nutrients for subsequent liquid fertilizer preparation. Bacillus further promotes the synthesis of these nutrient small molecules. To ensure the effective supply of nutrients, the ion exchange resin method is used to extract nutrients from the treated waste liquid. After the strong acid cation exchange resin and the strong alkaline anion exchange resin are mixed in a suitable proportion, they are pre-treated by soaking and washing, and can accurately adsorb various nutrients in the waste liquid, such as nitrogen, phosphorus, potassium, and trace elements such as iron and zinc. Then, through elution with an eluent, high-purity nutrients can be collected for the precise allocation of subsequent liquid fertilizers, ensuring that the liquid fertilizer has comprehensive nutrients and accurate content, which can better meet the growth needs of plants and greatly improve the resource utilization rate of the tyvalocin waste liquid. 2. The present invention forms a solution of chitosan and sodium alginate into a specific concentration, and then uses an electrostatic drip method and applies a certain electric field strength to cross-link them to form nano-scale gel particles, thereby constructing a stable gel system framework. Subsequently, temperature-sensitive N-isopropylacrylamide (NIPAAm) and pH-sensitive acrylic acid (AA) are introduced and grafted onto the surface of the gel particles in a specific proportion, and the free radical polymerization reaction is used to make the gel particles have intelligent response characteristics. This intelligent response nanogel system plays an important role in fertilizers. On the one hand, under different temperature and pH environments, it can respond to changes in external conditions, effectively maintain the stability of its own structure, and thus ensure the integrity of the fertilizer. The structure of the nanogel is not excessively disturbed by external factors. When the temperature fluctuates or the soil pH changes, the gel system can adjust itself to prevent the fertilizer nutrients from being lost or becoming ineffective due to environmental changes. On the other hand, the nanogel system is immersed in an ethanol solution containing a variety of nutrients. The porous structure of the gel is used to achieve efficient loading of nutrients. During the use of the fertilizer, these loaded nutrients can be released slowly and continuously, avoiding the waste caused by a one-time large-scale release of nutrients and the possible fertilizer damage to plants. At the same time, the fertilizer can continuously and stably provide nutrients to plants for a long time, effectively improving the stability of the fertilizer, which is more conducive to the long-term healthy growth of plants. 3. The present invention selects nano-scale activated carbon with a specific surface area within a specific range as the basic material. Its rich pore structure provides sufficient space for subsequent adsorption. Manganese dioxide nanoparticles with a particle size that meets the requirements and a precise ratio of cyclodextrin molecules to modifying groups, as well as specially modified cyclodextrin derivatives, together constitute a key combination. On this basis, they are grafted onto the surface of activated carbon by a chemical grafting method. The coupling agent plays an important role in this process. The coupling agent can form a chemical bond between the manganese dioxide nanoparticles, the cyclodextrin derivatives and the activated carbon, effectively enhancing the connection strength between them and ensuring the stability of the composite material structure. , so that it can maintain good performance in the subsequent reaction process with the tyvalosin waste liquid. When the multifunctional composite material comes into contact with the tyvalosin waste liquid, the activated carbon uses its own adsorption properties to physically adsorb some impurities and organic pollutants in the waste liquid. The manganese dioxide nanoparticles participate in the decomposition reaction of complex organic pollutants by virtue of their chemical activity. The cyclodextrin derivatives rely on their special affinity to specifically adsorb tyvalosin. Subsequently, after a series of operations such as centrifugation and elution, not only can high-purity tyvalosin be efficiently recovered, but the waste liquid can also be further treated to effectively remove residual impurities and adjust its pH value, making it closer to a reusable state. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Schematic diagram of the method steps in an embodiment of the present invention. DETAILED DESCRIPTION

[0014] The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention.

[0015] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0016] Please see attached Figure 1 The present invention provides a composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid, and the composition optimization method for preparing liquid fertilizer comprises the following specific steps: Step 1: Select nano-scale activated carbon as a basic material, prepare manganese dioxide nanoparticles for standby use, then prepare a modified cyclodextrin derivative, and then graft the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives onto the surface of the activated carbon by a chemical grafting method to complete the preparation of the multifunctional composite material, and then pre-treat the tyvalosin waste liquid, put the tyvalosin waste liquid and the prepared multifunctional composite material into a reaction container with a stirring device and temperature control for stirring reaction, during which the composite material specifically adsorbs tyvalosin, and at the same time, preliminarily decomposes and adsorbs and removes organic pollutants in the waste liquid; Step 2: After the reaction is completed, the mixed liquid in the reaction container is collected, centrifuged by a centrifuge, eluted with an ethanol solution, the eluate is collected after elution and processed to obtain high-purity tyvalocin, and the waste liquid obtained after centrifugation is filtered, the pH value is adjusted, and then collected for later use; Step 3: construct a microbial flora system of Pseudomonas bacteria, actinomycetes and Bacillus, then connect the treated waste liquid to the microbial flora system for reaction, and after the reaction, centrifuge and collect for later use; Step 4: After the reaction is completed, the microbial cells and the treated waste liquid are separated by centrifugation, and the nutrients are extracted from the separated waste liquid by an ion exchange resin method, and then deionized water is used as a base liquid for preliminary preparation of liquid fertilizer; Step 5: prepare the nanogel system, add the nanogel system into the preliminary liquid fertilizer solution, add high-purity tyvalocin, and stir and mix thoroughly to form the final liquid fertilizer product.

[0017] In one embodiment of the present invention: in step 1, the selected basic material nano-scale activated carbon has a specific surface area of ​​1000m 2 / g-1500m 2 / g, the prepared manganese dioxide nanoparticles have a particle size of 20nm-50nm and the ratio of cyclodextrin molecules to modifying groups is 1:2, the ratio of cyclodextrin molecules to modifying groups on the surface of manganese dioxide nanoparticles in the prepared modified cyclodextrin derivatives reaches 1:2, and the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives are grafted onto the surface of activated carbon by a chemical grafting method. The specific operation is as follows: under nitrogen protection, the activated carbon is placed in a mixed solution containing cyclodextrin derivatives and manganese dioxide nanoparticles, wherein The concentration of cyclodextrin derivative is 0.3mol / L-0.7mol / L, the concentration of manganese dioxide nanoparticles is 0.2mol / L-0.4mol / L, and then 4%-6% of the mass of activated carbon as coupling agent 3-(trimethoxysilyl)propyl isocyanate is added for stirring reaction, and the reaction is stirred at 45°C-65°C for 20h-28h. After the reaction is completed, the composite material is washed with deionized water and anhydrous ethanol for 3-5 times in turn, and then vacuum dried at 55°C-85°C for 10h-30h.

[0018] In one embodiment of the present invention: in step 1, the tyvalosin waste liquid and the prepared multifunctional composite material are placed in a reaction vessel with a stirring device and temperature control in a volume ratio of 1:3-5, the reaction temperature is set to 30°C-40°C, the stirring speed is 300r / min-500r / min, and the reaction time is 2h-3h.

[0019] In one embodiment of the present invention: in step 2, the centrifugal speed is set to 4000r / min-6000r / min, the centrifugation time is 10min-20min, and an ethanol solution with a concentration of 60%-80% is used as an eluent. The mass ratio of the eluent to the composite material adsorbed with tyvalocin is 4-6:1. After elution, the eluate is collected, concentrated under reduced pressure to 1 / 4-1 / 6 of the original volume at 35°C-55°C, and then dried in a vacuum drying oven for 18h-30h, the drying oven temperature is set to 40°C-60°C, and the filtration separation is performed using a filter membrane with a pore size of 0.2μm-0.3μm for filtration and impurity removal, and the pH value is adjusted to 6.0-7.5 with dilute hydrochloric acid and sodium hydroxide solution.

[0020] In one embodiment of the present invention: in step 3, Pseudomonas bacteria, actinomycetes and Bacillus are screened and inoculated into a culture medium according to a quantitative ratio of 1.5-1.8:1-2.5:3.3, wherein the components of the culture medium include glucose with a concentration of 15g / L-25g / L as a carbon source, ammonium chloride with a concentration of 3g / L-7g / L as a nitrogen source, and a trace element solution containing calcium, magnesium, iron and zinc, and the concentration of each trace element is 0.05g / L-0.15g / L, and the culture is carried out at a temperature of 25°C-35°C and a ventilation volume of 0.3L / min-1.2L / min for 3-5 days, and then the waste liquid treated in step 2 is connected to the reaction container where the cultured microbial flora system is located, and the volume ratio of the waste liquid to the microbial flora is controlled at 1:2-3, and the reaction is stirred at a temperature of 25°C-35°C and a stirring speed of 200r / min-300r / min for 5-7 days.

[0021] In one embodiment of the present invention: in step 4, the microbial cells and the treated waste liquid are centrifuged at a controlled speed of 3000r / min-5000r / min, the centrifugation time is 15min-25min, and the separated waste liquid is subjected to ion exchange resin method for nutrient extraction. The specific process is as follows: a strongly acidic cation exchange resin and a strongly basic anion exchange resin are mixed in a volume ratio of 0.8-1.2:1, soaked in deionized water and stirred for 2h-4h, repeatedly rinsed 3-5 times until the conductivity is less than 10μS / cm, the mixed resin is loaded into an ion exchange column, and the waste liquid slowly flows through the resin layer at a flow rate of 1mL / min-3mL / min. After the waste liquid has completely flowed through, it is rinsed with deionized water accounting for 10%-20% of the volume of the waste liquid, and 1mol / L-2mol / L hydrochloric acid is used as an eluent, and the nutrients are eluted through the resin at a flow rate of 1mL / min-3mL / min.

[0022] In one embodiment of the present invention: in step 4, the liquid fertilizer is initially prepared with deionized water as the base liquid, ammonium nitrate is added to make the concentration of nitrogen in the base liquid reach 100 mg / L-200 mg / L, potassium dihydrogen phosphate is added to make the concentration of phosphorus in the base liquid 50 mg / L-100 mg / L, potassium nitrate is added to ensure that the concentration of potassium in the base liquid is 150 mg / L-300 mg / L, and composite trace element fertilizers are added to make the concentrations of each trace element in the base liquid respectively: iron element 0.5-2mg / L, zinc 0.2-1mg / L, manganese 0.3-1.5mg / L, copper 0.1-0.5mg / L, boron 0.5-2mg / L and molybdenum 0.05-0.2mg / L, the extracted eluent containing high-purity nutrients is added to the base liquid at 100g-150g per liter of deionized water, and 3%-7% urea by volume of deionized water is added to supplement nitrogen, and 2%-4% superphosphate by volume of deionized water is added to supplement phosphorus.

[0023] In one embodiment of the present invention: in step 5, chitosan is dissolved in a dilute acetic acid solution with a concentration of 0.8%-1.2% to prepare a 2.5% w / v-3.5% w / v chitosan solution, sodium alginate is dissolved in deionized water to prepare a 3.5% w / v-4.5% w / v sodium alginate solution, and the chitosan solution is added dropwise to the sodium alginate solution by an electrostatic drip method and an electric field strength of 600 V / cm-1000 V / cm is applied. , N-isopropylacrylamide (NIPAAm) is grafted onto the surface at a mass ratio of 1:4-6 to the nanogel particles, and acrylic acid (AA) is grafted onto the surface at a mass ratio of 1:5-7 to the nanogel particles. The amount of initiator potassium persulfate is 0.3%-0.7% of the total mass of the monomers. The reaction is carried out at 50℃-70℃ for 2-4h, and then the nanogel system is immersed in an ethanol solution with a concentration of 40%-60% for 18h-30h.

[0024] In one embodiment of the present invention: in step 5, after obtaining the nanogel system, the prepared nanogel system is finally added to the preliminary liquid fertilizer solution in an amount of 3%-7% of the volume of the preliminary liquid fertilizer solution, and the high-purity tyvalocin obtained in step 2 is added to the preliminary liquid fertilizer solution in an amount of 5%-8% of the volume of the preliminary liquid fertilizer solution, and the mixture is fully stirred and mixed for 1h-2h at a temperature of 25°C-30°C and a stirring speed of 150r / min-250r / min.

[0025] In one embodiment of the present invention: in step 1, manganese dioxide nanoparticles with a particle size of 20-50 nm and a ratio of cyclodextrin molecules to modifying groups on the surface of the manganese dioxide nanoparticles of 1:2 are prepared. Specifically, the ratio modification can be achieved by a specific chemical synthesis method. The manganese dioxide nanoparticles are first subjected to surface activation treatment, and then reacted with a reaction solution containing a specific ratio of cyclodextrin derivatives and modifying groups under appropriate conditions to ensure that the ratio of cyclodextrin molecules to modifying groups on the surface of the manganese dioxide nanoparticles is finally 1:2. At the same time, a specially modified cyclodextrin derivative is prepared. The special modification here refers to the modification of the ratio by The chemical grafting reaction is achieved by grafting specific functional groups onto cyclodextrin molecules. The specific operation is as follows: select cyclodextrin raw materials, dissolve them in the solvent dimethyl sulfoxide to form a solution with a concentration of 0.2mol / L-0.5mol / L, and then add the modification reagent (halogenated hydrocarbons containing specific functional groups, and the molar ratio of halogenated hydrocarbons to cyclodextrin molecules is 1:1-1.5:1), and react at a temperature of 40℃-60℃ and a stirring speed of 200r / min-400r / min for 12h-24h, thereby successfully grafting specific functional groups onto the cyclodextrin molecules and completing the special modification of cyclodextrin derivatives.

[0026] In one embodiment of the present invention: in step 2, after eluting the composite material adsorbed with tyvalosin with an ethanol solution, ultrafiltration is performed before collecting the eluate, and the eluate is filtered using an ultrafiltration membrane with a molecular weight cutoff of 1000Da-3000Da to remove possible macromolecular impurities and microparticles of the composite material that have not been completely eluted, thereby further improving the purity of the obtained tyvalosin, ensuring that the nutritional components can be more accurately regulated when it is subsequently used in the preparation of liquid fertilizer, and avoiding the influence of impurities on the quality of the liquid fertilizer.

[0027] In one embodiment of the present invention: in step five, before adding the nanogel system to the preliminary liquid fertilizer solution, the nanogel system is first subjected to surface modification treatment, specifically, the nanogel system is immersed in a mixed solution containing polyvinyl alcohol (PVA) with a mass concentration of 0.1%-0.3% and carboxymethyl cellulose (CMC) with a mass concentration of 0.05%-0.15%, and stirred and immersed at 30°C-40°C for 2h-4h. After the surface-modified nanogel system is added to the liquid fertilizer solution, it can better interact with the nutrients in the liquid fertilizer, enhance its stability in the solution, and prevent the nanogel system from agglomerating during storage or use, thereby more effectively achieving the slow release of nutrients, extending the duration of the fertilizer effect of the liquid fertilizer, and improving the quality and use effect of the liquid fertilizer product.

[0028] Example 1, please refer to the attached Figure 1, selected nano-scale activated carbon with a specific surface area of ​​1500m² / g as the basic material, prepared manganese dioxide nanoparticles with a particle size of 50nm and a ratio of cyclodextrin molecules to modifying groups of 1:2, and prepared modified cyclodextrin derivatives (so that the cyclodextrin molecules on the surface of manganese dioxide nanoparticles and the modifying groups reached 1:2), and the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives were grafted onto the surface of the activated carbon by a chemical grafting method. The specific operation was to place the activated carbon in a mixed solution containing the above-mentioned cyclodextrin derivatives and manganese dioxide nanoparticles under nitrogen protection, wherein the concentration of the cyclodextrin derivatives was 0.7mol / L and the concentration of the manganese dioxide nanoparticles was 2.5mol / L. The concentration was 0.4 mol / L, and then 6% of the mass of activated carbon coupling agent 3-(trimethoxysilyl)propyl isocyanate was added for stirring reaction. The reaction was stirred at 65°C for 28 hours. After the reaction, the composite material was washed with deionized water and anhydrous ethanol for 5 times, and then vacuum dried at 85°C for 30 hours to complete the preparation of the multifunctional composite material. Then, the tyvalosin waste liquid was pretreated. The tyvalosin waste liquid and the prepared multifunctional composite material were placed in a reaction vessel with a stirring device and temperature control in a volume ratio of 1:5. The reaction temperature was set to 40°C, the stirring speed was 500r / min, and the reaction time was 3h. In this process, the composite material was specifically The mixture is subjected to the step of adsorbing tyvalosin, and the organic pollutants in the waste liquid are preliminarily decomposed and adsorbed and removed. After the reaction is completed, the mixed liquid in the reaction container is collected, and the composite material in the mixed liquid is separated and collected from the waste liquid by centrifugation. The centrifugal speed is set to 6000r / min, the centrifugal time is 20min, and an ethanol solution with a concentration of 80% is used as an eluent. The eluent is eluted at a mass ratio of 6:1 between the eluent and the composite material adsorbed with tyvalosin. After elution, the eluate is collected, concentrated under reduced pressure at 55°C to 1 / 4 of the original volume, and then dried in a vacuum drying oven for 30h, and the drying oven temperature is set to 60°C to obtain high-purity tyvalosin. After that, for The waste liquid obtained after centrifugation was filtered and filtered with a filter membrane with a pore size of 0.3 μm to remove residual fine impurities, and then the pH value was adjusted to 7.5 with dilute hydrochloric acid and sodium hydroxide solution, and then collected for use, a microbial flora system was constructed, and Pseudomonas bacteria, actinomycetes and Bacillus were screened out and inoculated into a culture medium according to a quantitative ratio of 1.8:2.5:3.3. The components of the culture medium included 25 g / L glucose as a carbon source, 7 g / L ammonium chloride as a nitrogen source, and a trace element solution containing calcium, magnesium, iron and zinc, and the concentration of each trace element was 0.15 g / L. The culture medium was incubated at a temperature of 35°C and a ventilation volume of 1.2L / min for 5 days, so that the three fungi cooperate with each other to form a stable microbial flora system, the waste liquid treated in step 2 is connected to the reaction container where the cultured microbial flora system is located, the volume ratio of the waste liquid to the microbial flora is controlled at 1:3, and the reaction is stirred at a stirring speed of 300r / min at a temperature of 35°C for 7 days and then collected for use. During this period, Pseudomonas bacteria gradually decompose the complex organic pollutants in the waste liquid into carbon dioxide, water and simple organic acids through mineralization, and actinomycetes use the enzymes they secrete to enzymatically convert tyvalcin into small molecule compounds containing nutrients such as nitrogen, phosphorus and potassium that can be absorbed and utilized by plants. Bacillus further promotes the synthesis and stabilization of these nutrient small molecules. After the reaction, the microbial cells and the treated waste liquid are separated by centrifugation. The centrifugal speed is controlled to be 5000r / min and the centrifugal time is 25min. The separated waste liquid is subjected to ion exchange resin method for nutrient extraction. Specifically, the strongly acidic cation exchange resin and the strongly basic anion exchange resin are first mixed in a volume ratio of 1.2:1, and then immersed and stirred for 4h in deionized water, and then repeatedly rinsed 5 times until the conductivity is less than 10μS / cm. The mixed resin is loaded into the ion exchange column, and the treated waste liquid is slowly passed through the resin layer at a flow rate of 3mL / min. During this process, stirring is performed to ensure that the waste liquid and the resin Full contact, after all the waste liquid flows through, rinse with deionized water accounting for 20% of the volume of the waste liquid, then use 2mol / L hydrochloric acid as eluent, flow through the resin at a flow rate of 3mL / min to elute the nutrients, and then collect the eluate containing high-purity nutrients flowing out of the ion exchange column, and then conduct preliminary preparation of liquid fertilizer, using deionized water as the base liquid, adding ammonium nitrate to make the concentration of nitrogen in the base liquid reach 200mg / L, adding potassium dihydrogen phosphate to make the concentration of phosphorus in the base liquid 100mg / L, and adding potassium nitrate to ensure that the concentration of potassium in the base liquid is 300mg / L, and adding composite trace element fertilizer containing trace elements of iron, zinc, manganese, copper, boron and molybdenum. The concentrations of various trace elements in the base liquid are as follows: 2 mg / L iron, 1 mg / L zinc, 1.5 mg / L manganese, 0.5 mg / L copper, 2 mg / L boron and 0.2 mg / L molybdenum. The eluent containing high-purity nutrients is added to the base liquid at 150 g per liter of deionized water. Urea is added at a volume of 7% of the deionized water volume to supplement nitrogen, and superphosphate is added at a volume of 4% of the deionized water volume to supplement phosphorus to prepare a preliminary liquid fertilizer solution. Chitosan is dissolved in a 1.2% dilute acetic acid solution to prepare a 3.5% w / v chitosan solution. At the same time, sodium alginate is dissolved in deionized water to prepare a 4.5% w / v sodium alginate solution, chitosan solution was added dropwise into the sodium alginate solution by electrostatic drop method and an electric field strength of 1000 V / cm was applied to crosslink the polymers in the two solutions to form nano-scale gel particles, and then temperature-sensitive N-isopropylacrylamide (NIPAAm) was grafted onto the surface at a mass ratio of 1:6 to the nanogel particles, and acid-sensitive acrylic acid (AA) was grafted onto the surface at a mass ratio of 1:7 to the nanogel particles. The amount of initiator potassium persulfate was 0.7% of the total mass of the monomers. The reaction was carried out at 70°C for 4 hours, and then the nanogel was The system was immersed in a 60% ethanol solution for 30 hours, and the porous structure of the gel was used to achieve efficient loading of nutrients to obtain a nanogel system. Finally, the prepared nanogel system was added to the preliminary liquid fertilizer solution, and the added amount was 7% of the volume of the preliminary liquid fertilizer solution. The high-purity tyvalosin obtained in step 2 was added to the preliminary liquid fertilizer solution, and the addition amount of the high-purity tyvalosin was 8% of the volume of the preliminary liquid fertilizer solution. The mixture was fully stirred and mixed for 2 hours at a temperature of 30°C and a stirring speed of 250r / min to ensure that the nanogel was evenly dispersed in the liquid fertilizer solution to form the final liquid fertilizer product. .

[0029] Example 2, please refer to the attached Figure 1, select nano-scale activated carbon with a specific surface area of ​​1000m² / g as the basic material, prepare manganese dioxide nanoparticles with a particle size of 20nm and a ratio of cyclodextrin molecules to modifying groups of 1:2, and prepare modified cyclodextrin derivatives (so that the cyclodextrin molecules on the surface of manganese dioxide nanoparticles and the modifying groups reach 1:2), and graft the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives to the surface of the activated carbon by a chemical grafting method. The specific operation is to place the activated carbon in a mixed solution containing the above-mentioned cyclodextrin derivatives and manganese dioxide nanoparticles under nitrogen protection, wherein the concentration of the cyclodextrin derivatives is 0.3mol / L, and the concentration of the manganese dioxide nanoparticles is 1.5mol / L. The concentration was 0.2 mol / L, and then 4% of the mass of activated carbon coupling agent 3-(trimethoxysilyl)propyl isocyanate was added for stirring reaction. The reaction was stirred at 45°C for 20 hours. After the reaction, the composite material was washed with deionized water and anhydrous ethanol for 3 times, and then vacuum dried at 55°C for 10 hours to complete the preparation of the multifunctional composite material. Then, the tyvalocin waste liquid was pretreated. The tyvalocin waste liquid and the prepared multifunctional composite material were placed in a reaction vessel with a stirring device and temperature control in a volume ratio of 1:3. The reaction temperature was set to 30°C, the stirring speed was 300r / min, and the reaction time was 2h. During this process, the composite material The invention discloses a method for specifically adsorbing tyvalosin and performing preliminary decomposition and adsorption removal of organic pollutants in the waste liquid. After the reaction is completed, the mixed liquid in the reaction container is collected, and the composite material in the mixed liquid is separated and collected from the waste liquid by centrifugation. The centrifugal speed is set to 4000 r / min, the centrifugal time is set to 10 min, and a 60% ethanol solution is used as an eluent. The eluent is eluted at a mass ratio of 6:1 between the eluent and the composite material adsorbed with tyvalosin. The eluent is collected, concentrated under reduced pressure at 35°C to 1 / 6 of the original volume, and then dried in a vacuum drying oven for 18 hours. The drying oven temperature is set to 40°C to obtain high-purity tyvalosin. The waste liquid obtained after centrifugal separation was filtered, and a filter membrane with a pore size of 0.2 μm was used to filter and remove impurities to remove residual fine impurities, and then the pH value was adjusted to 6.0 with dilute hydrochloric acid and sodium hydroxide solution, and then collected for use, a microbial flora system was constructed, and Pseudomonas bacteria, actinomycetes and Bacillus were screened out, and they were inoculated into a culture medium according to a quantitative ratio of 1.5:1:3.3. The components of the culture medium included glucose with a concentration of 15 g / L as a carbon source, ammonium chloride with a concentration of 3 g / L as a nitrogen source, and a trace element solution containing calcium, magnesium, iron, and zinc, and the concentration of each trace element was 0.05 g / L. The culture medium was incubated at a temperature of 25°C and a ventilation volume of 0.The mixture was cultured at 3 L / min for 3 days to allow the three fungi to cooperate with each other and form a stable microbial flora system. The waste liquid treated in step 2 was connected to the reaction container where the cultured microbial flora system was located. The volume ratio of the waste liquid to the microbial flora was controlled at 1:2. The mixture was stirred at 200 r / min at a temperature of 25°C for 5 days. During this period, Pseudomonas bacteria gradually decomposed the complex organic pollutants in the waste liquid into carbon dioxide, water and simple organic acids through mineralization. Actinomycetes used the enzymes they secreted to enzymatically convert tyvalcin into small molecule compounds containing nutrients such as nitrogen, phosphorus and potassium that can be absorbed and utilized by plants. Bacillus To further promote the synthesis and stability of these nutrient small molecules, the microbial cells and the treated waste liquid were separated by centrifugation after the reaction. The centrifugal speed was controlled to be 3000r / min and the centrifugal time was 15min. The nutrient components of the separated waste liquid were extracted by ion exchange resin method. Specifically, the strong acid cation exchange resin and the strong alkaline anion exchange resin were mixed at a volume ratio of 0.8:1, and then immersed and stirred for 2h in deionized water, and then repeatedly rinsed 3 times until the conductivity was less than 10μS / cm. The mixed resin was loaded into the ion exchange column, and the treated waste liquid was slowly passed through the resin layer at a flow rate of 1mL / min. During this process, it was stirred to ensure that the waste liquid was fully in contact with the resin. After all the waste liquid has flowed through, it is rinsed with deionized water accounting for 10% of the volume of the waste liquid. Then, 1 mol / L hydrochloric acid is used as an eluent to elute the nutrients through the resin at a flow rate of 1 mL / min. Then, the eluate containing high-purity nutrients flowing out of the ion exchange column is collected, and then the liquid fertilizer is initially prepared. Deionized water is used as the base liquid, and ammonium nitrate is added to make the concentration of nitrogen in the base liquid reach 100 mg / L. Potassium dihydrogen phosphate is added to make the concentration of phosphorus in the base liquid 50 mg / L. Potassium nitrate is added to ensure that the concentration of potassium in the base liquid is 150 mg / L. At the same time, a composite trace element fertilizer containing trace elements of iron, zinc, manganese, copper, boron, and molybdenum is added to make each trace element. The concentrations of the elements in the base solution are: 0.5 mg / L iron, 0.2 mg / L zinc, 0.3 mg / L manganese, 0.1 mg / L copper, 0.5 mg / L boron and 0.05 mg / L molybdenum. The extracted eluent containing high-purity nutrients is added to the base solution at 100 g per liter of deionized water, and 3% urea by volume of deionized water is added to supplement nitrogen, and 2% superphosphate by volume of deionized water is added to supplement phosphorus to prepare a preliminary liquid fertilizer solution. Chitosan is dissolved in a 0.8% dilute acetic acid solution to prepare a 2.5% w / v chitosan solution, and sodium alginate is dissolved in deionized water to prepare a 3.5% w / v sodium alginate solution, chitosan solution was added dropwise into the sodium alginate solution by electrostatic drop method and an electric field strength of 600 V / cm was applied to crosslink the polymers in the two solutions to form nano-scale gel particles, and then temperature-sensitive N-isopropylacrylamide (NIPAAm) was grafted onto the surface at a mass ratio of 1:4 to the nanogel particles, and acid-base-sensitive acrylic acid (AA) was grafted onto the surface at a mass ratio of 1:5 to the nanogel particles. The amount of potassium persulfate was 0.3% of the total mass of the monomers, and the reaction was carried out at 50 ° C for 2 hours, and then the nanogel system was immersed In a 40% ethanol solution for 18 hours, the porous structure of the gel is used to achieve efficient loading of nutrients to obtain a nanogel system. Finally, the prepared nanogel system is added to the preliminary liquid fertilizer solution, and the added amount is 3% of the volume of the preliminary liquid fertilizer solution. The high-purity tyvalosin obtained in step 2 is added to the preliminary liquid fertilizer solution, and the added amount of the high-purity tyvalosin is 5% of the volume of the preliminary liquid fertilizer solution. The mixture is fully stirred and mixed for 1 hour at a temperature of 25°C and a stirring speed of 150r / min to ensure that the nanogel is evenly dispersed in the liquid fertilizer solution to form the final liquid fertilizer product. .

[0030] According to the above two groups of embodiments, it can be concluded that by carefully selecting and accurately preparing materials such as nano-scale activated carbon, manganese dioxide nanoparticles, and cyclodextrin derivatives, and strictly controlling the parameters of each link, the multifunctional composite material can effectively treat the tylvalosin waste liquid, specifically adsorb tylvalosin, and decompose and remove organic pollutants. Subsequently, high-purity tylvalosin is obtained through specific separation and recovery operations. The microbial flora system synergistically transforms the waste liquid components, and the ion exchange resin method accurately extracts nutrients for liquid fertilizer preparation. Combined with the intelligent responsive nanogel system, the stability and fertilizer efficiency of the liquid fertilizer are guaranteed. The entire process of the patent of the present invention, with the help of multiple technologies and precise parameters in each step, achieves a complete process from waste liquid treatment to high-quality product output, which can achieve the effect of efficient resource utilization and high-quality product presentation, and has obvious technical advantages and broad application prospects.

[0031] Although the present invention is disclosed as above in terms of preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art may 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 embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for optimizing the composition of liquid fertilizer prepared from tyvalocin waste liquid, characterized in that: The composition optimization method for preparing liquid fertilizer comprises the following specific steps: Step 1: Select nano-scale activated carbon as a base material, prepare manganese dioxide nanoparticles for standby use, then prepare a modified cyclodextrin derivative, and then graft the manganese dioxide nanoparticles and the specially modified cyclodextrin derivative to the surface of the activated carbon by a chemical grafting method to complete the preparation of the multifunctional composite material, and then pretreat the tyvalosin waste liquid, and put the tyvalosin waste liquid and the prepared multifunctional composite material into a reaction container with a stirring device and temperature control for stirring reaction; Step 2: After the reaction is completed, the mixed liquid in the reaction container is collected, centrifuged by a centrifuge, eluted with an ethanol solution, the eluate is collected after elution and processed to obtain high-purity tyvalocin, and the waste liquid obtained after centrifugation is filtered, the pH value is adjusted, and then collected for later use; Step 3: construct a microbial flora system of Pseudomonas bacteria, actinomycetes and Bacillus, then connect the treated waste liquid to the microbial flora system for reaction, and after the reaction, centrifuge and collect for later use; Step 4: After the reaction is completed, the microbial cells and the treated waste liquid are separated by centrifugation, and the nutrients are extracted from the separated waste liquid by an ion exchange resin method, and then deionized water is used as a base liquid for preliminary preparation of liquid fertilizer; Step 5: prepare the nanogel system, add the nanogel system into the preliminary liquid fertilizer solution, add high-purity tyvalocin, and stir and mix thoroughly to form the final liquid fertilizer product.

2. The composition optimization method for preparing liquid fertilizer from a tyvalocin waste liquid according to claim 1, characterized in that: In the step 1, the specific surface area of ​​the selected basic material nano-scale activated carbon is 1000m 2 / g-1500m 2 / g, the prepared manganese dioxide nanoparticles have a particle size of 20nm-50nm and the ratio of cyclodextrin molecules to modifying groups is 1:2, the ratio of cyclodextrin molecules to modifying groups on the surface of manganese dioxide nanoparticles in the prepared modified cyclodextrin derivatives reaches 1:2, and the manganese dioxide nanoparticles and the specially modified cyclodextrin derivatives are grafted onto the surface of activated carbon by a chemical grafting method. The specific operation is as follows: under nitrogen protection, the activated carbon is placed in a mixed solution containing cyclodextrin derivatives and manganese dioxide nanoparticles, wherein The concentration of cyclodextrin derivative is 0.3mol / L-0.7mol / L, the concentration of manganese dioxide nanoparticles is 0.2mol / L-0.4mol / L, and then 4%-6% of the mass of activated carbon as coupling agent 3-(trimethoxysilyl)propyl isocyanate is added for stirring reaction, and the reaction is stirred at 45°C-65°C for 20h-28h. After the reaction is completed, the composite material is washed with deionized water and anhydrous ethanol for 3-5 times in turn, and then vacuum dried at 55°C-85°C for 10h-30h.

3. The composition optimization method for preparing liquid fertilizer from a tyvalocin waste liquid according to claim 1, characterized in that: In the step 1, the tyvalosin waste liquid and the prepared multifunctional composite material are placed in a reaction vessel with a stirring device and temperature control according to a volume ratio of 1:3-5, the reaction temperature is set to 30°C-40°C, the stirring speed is 300r / min-500r / min, and the reaction time is 2h-3h.

4. The composition optimization method for preparing liquid fertilizer from a tyvalocin waste liquid according to claim 1, characterized in that: In the step 2, the centrifugal speed is set to 4000r / min-6000r / min, the centrifugal time is 10min-20min, and an ethanol solution with a concentration of 60%-80% is used as an eluent. The eluent is eluted at a mass ratio of 4-6:1 between the eluent and the composite material adsorbed with tyvalocin. After elution, the eluate is collected, concentrated under reduced pressure to 1 / 4-1 / 6 of the original volume at 35°C-55°C, and then dried in a vacuum drying oven for 18h-30h, the drying oven temperature is set to 40°C-60°C, and the filtration separation is performed using a filter membrane with a pore size of 0.2μm-0.3μm for filtration and impurity removal, and the pH value is adjusted to 6.0-7.5 with dilute hydrochloric acid and sodium hydroxide solution.

5. The composition optimization method for preparing liquid fertilizer from a tyvalocin waste liquid according to claim 1, characterized in that: In the step 3, Pseudomonas bacteria, actinomycetes and Bacillus are screened out, and they are inoculated into a culture medium according to a quantitative ratio of 1.5-1.8:1-2.5:3.

3. The components of the culture medium include glucose with a concentration of 15g / L-25g / L as a carbon source, ammonium chloride with a concentration of 3g / L-7g / L as a nitrogen source, and a trace element solution containing calcium, magnesium, iron and zinc, and the concentration of each trace element is 0.05g / L-0.15g / L. The culture is carried out at a temperature of 25°C-35°C and a ventilation volume of 0.3L / min-1.2L / min for 3-5 days, and then the waste liquid treated in step 2 is connected to the reaction container where the cultured microbial flora system is located, and the volume ratio of the waste liquid to the microbial flora is controlled at 1:2-3, and the reaction is stirred at a temperature of 25°C-35°C and a stirring speed of 200r / min-300r / min for 5-7 days.

6. The composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid according to claim 1, characterized in that: In the step 4, the microbial cells and the treated waste liquid are centrifuged at a controlled speed of 3000r / min-5000r / min, the centrifugation time is 15min-25min, and the separated waste liquid is subjected to ion exchange resin method for nutrient extraction. The specific process is as follows: a strongly acidic cation exchange resin and a strongly basic anion exchange resin are mixed in a volume ratio of 0.8-1.2:1, soaked in deionized water and stirred for 2h-4h, repeatedly rinsed 3-5 times until the conductivity is less than 10μS / cm, the mixed resin is loaded into an ion exchange column, the waste liquid slowly flows through the resin layer at a flow rate of 1mL / min-3mL / min, and after all the waste liquid flows through, it is rinsed with deionized water accounting for 10%-20% of the volume of the waste liquid, and 1mol / L-2mol / L hydrochloric acid is used as an eluent, and the nutrients are eluted through the resin at a flow rate of 1mL / min-3mL / min.

7. The composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid according to claim 1, characterized in that: In the fourth step, the liquid fertilizer is initially prepared with deionized water as the base liquid, ammonium nitrate is added to make the concentration of nitrogen in the base liquid reach 100 mg / L-200 mg / L, potassium dihydrogen phosphate is added to make the concentration of phosphorus in the base liquid 50 mg / L-100 mg / L, potassium nitrate is added to ensure that the concentration of potassium in the base liquid is 150 mg / L-300 mg / L, and composite trace element fertilizers are added to make the concentrations of each trace element in the base liquid respectively: iron 0.5-2 mg / L, zinc 0.2-1mg / L, manganese 0.3-1.5mg / L, copper 0.1-0.5mg / L, boron 0.5-2mg / L and molybdenum 0.05-0.2mg / L, the extracted eluent containing high-purity nutrients is added to the base liquid at 100g-150g per liter of deionized water, and 3%-7% of the volume of deionized water is added with urea to supplement nitrogen, and 2%-4% of the volume of deionized water is added with superphosphate to supplement phosphorus.

8. The composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid according to claim 1, characterized in that: In the step 5, chitosan is dissolved in a dilute acetic acid solution with a concentration of 0.8%-1.2% to prepare a chitosan solution with a concentration of 2.5% w / v-3.5% w / v, sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a concentration of 3.5% w / v-4.5% w / v, the chitosan solution is added dropwise to the sodium alginate solution by an electrostatic drip method and an electric field strength of 600V / cm-1000V / cm is applied, N-isopropylacrylamide (NIPAAm) is grafted onto the surface at a mass ratio of 1:4-6 to the nanogel particles, acrylic acid (AA) is grafted onto the surface at a mass ratio of 1:5-7 to the nanogel particles, the initiator potassium persulfate is used in an amount of 0.3%-0.7% of the total mass of the monomers, the reaction is carried out at 50°C-70°C for 2-4h, and then the nanogel system is immersed in an ethanol solution with a concentration of 40%-60% for 18h-30h.

9. The composition optimization method for preparing liquid fertilizer from tyvalocin waste liquid according to claim 1, characterized in that: In the step 5, after obtaining the nanogel system, the prepared nanogel system is finally added to the preliminary liquid fertilizer solution in an amount of 3%-7% of the volume of the preliminary liquid fertilizer solution, and the high-purity tyvalocin obtained in step 2 is added to the preliminary liquid fertilizer solution in an amount of 5%-8% of the volume of the preliminary liquid fertilizer solution, and the mixture is fully stirred and mixed for 1h-2h at a temperature of 25°C-30°C and a stirring speed of 150r / min-250r / min.

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