Method for preparing organic fertilizer by anaerobic fermentation of tylosin mushroom dregs

Abstract

The invention relates to the field of fertilizers, in particular to a method for preparing an organic fertilizer by anaerobic fermentation of tylosin dregs, which comprises the following steps: (1) electron beam irradiation treatment; (2) adding the mushroom dreg powder into an ethanol solution, and treating with a coupling agent KH-550 to obtain aminated mushroom dregs; (3) preparing to obtain phosphorylated hydroxypropyl methyl cellulose; (4) mixing the aminated mushroom dregs and the phosphorylated hydroxypropyl methyl cellulose in an organic solvent for reaction to obtain phosphorylated hydroxypropyl methyl cellulose composite active mushroom dregs; and (5) composting to finally obtain the organic fertilizer. According to the organic fertilizer and the preparation method thereof, the tylosin mushroom dregs are subjected to modification treatment, anaerobic fermentation treatment and aerobic fermentation treatment, so that the content of antibiotic tylosin in the finally prepared organic fertilizer is greatly reduced, the industrial requirements can be met, the content of organic matters in soil can be increased, the soil structure can be improved, and the soil fertility can be improved; the plant growth is facilitated.

Description

Technical Field

[0001] The present invention relates to the field of fertilizers, and particularly relates to a method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue. Background Art

[0002] Mycelium residue refers to an organic substance produced during the fermentation of biomass materials. It usually refers to the microbial mixture remaining in domestic garbage such as distillers' grains, distillers' solubles, and food residues after fermentation. Mycelium residue contains substances such as complex flora, trace elements, and enzymes, and is a resource with high value. The raw materials for producing mycelium residue are usually biomass materials such as distillers' grains, distillers' solubles, and food residues. During the production process, the raw materials need to be treated to remove impurities and moisture, and then inoculated with strains and fermented. During the fermentation process, microorganisms carry out metabolic activities at appropriate temperatures, humidities, and pH values, and finally form mycelium residue. Antibiotic mycelium residue usually refers to the residue left after removing the active ingredients from the fermentation broth or culture medium during the production of antibiotics. These residues may include unused antibiotics, metabolites, cell debris, proteins, polysaccharides, lipids, and other bioactive substances.

[0003] Tylosin is a metabolite produced by submerged liquid fermentation of producing bacteria such as Streptomyces. During the submerged liquid fermentation production process, the producing bacteria not only synthesize the target product tylosin required by people, but also produce a large amount of mycelium. After the fermentation broth is treated and solid-liquid separated, the obtained solid phase is the mycelium and the culture medium substances that have not been fully utilized, and this substance is called tylosin fermentation mycelium residue, abbreviated as tylosin residue. Tylosin residue is rich in protein and vitamins and is a rich protein resource. In the past, some manufacturers dried it as feed protein. However, due to the presence of a certain amount of tylosin residue, abbreviated as "drug residue", after being ingested by animals as feed protein, it will form "antibiotic meat" and "antibiotic egg" products, causing direct harm to humans. Of course, there are also those who dry it and apply it as agricultural fertilizer, but if the drug residue is not solved, it will directly damage the soil microecological balance and induce the generation of drug-resistant strains. Especially, this mycelium residue contains more oil, and it often catches fire and burns during the drying process, making the treatment difficult. If it is directly discharged, it will cause serious environmental pollution and resource waste. Summary of the Invention

[0004] Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue.

[0005] The purpose of the present invention is achieved by the following technical solutions: A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue, comprising the following steps: (1) First, irradiate the tylosin mycelium residue with electron beam, place the obtained mycelium residue in an oven for drying, then grind and sieve it to obtain mycelium residue powder; (2) Put the mycelium residue powder into an ethanol solution, after sufficient dispersion, add coupling agent KH-550, heat up to reflux, then carry out heat preservation treatment. After the reaction is completed, filter, wash and dry to obtain amino-functionalized mycelium residue; (3) Dropwise add sodium hydroxide solution into sodium dihydrogen phosphate solution, adjust the pH of the system to 3.5 - 4.5, then add starch, hydroxypropyl methylcellulose, and 1,4-butanediol diglycidyl ether, and carry out cross-linking reaction. After the reaction ends, rinse three times with pure water and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mix the amino-functionalized mycelium residue and phosphorylated hydroxypropyl methylcellulose in an organic solvent, after stirring evenly, add aluminum chloride as a catalyst, heat up and carry out stirring reaction. After the reaction ends, remove the solvent under reduced pressure and dry to obtain phosphorylated hydroxypropyl methylcellulose composite active mycelium residue; (5) Thoroughly mix agricultural solid waste and phosphorylated hydroxypropyl methylcellulose composite active mycelium residue, adjust the water content of the mixture to 50% - 60%, then carry out anaerobic composting treatment. After the treatment ends, mix in aerobic bacteria and carry out aerobic composting treatment to finally obtain organic fertilizer.

[0006] Preferably, in step (1), the parameters of electron beam irradiation include: accelerator energy is 1.2 - 1.8 MeV, beam current is 50 - 70 mA; irradiation absorption dose is 10 - 50 kGy.

[0007] Preferably, in step (1), dry in the oven until the water content is lower than 5%; the temperature in the oven is 50 - 80 °C, and the mesh number of sieving is 50 - 100 mesh.

[0008] Preferably, in step (2), the mass fraction of the ethanol solution is 20% - 60%, and the mass ratio of the mycelium residue powder, coupling agent KH-550 and ethanol solution is 1:0.1 - 0.5:10 - 20.

[0009] Preferably, in step (2), the temperature of heat preservation treatment is 50 - 70 °C, and the time is 2 - 10 h.

[0010] Preferably, in step (3), the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 1 - 3:1:0.02 - 0.08:10 - 30.

[0011] Preferably, in step (3), the mass fraction of sodium dihydrogen phosphate solution is 15% - 25%, and the concentration of sodium hydroxide solution is 0.1 - 1 mol / L.

[0012] Preferably, in step (3), the temperature of the cross-linking reaction is 40-60°C and the time is 1-3 h.

[0013] Preferably, in step (4), the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and the organic solvent is 1:0.4-0.8:15-35.

[0014] Preferably, in step (4), the organic solvent is at least one of dioxane, tetrahydrofuran, chloroform and methylene chloride.

[0015] Preferably, in step (4), the addition amount of aluminum chloride is 3%-8% of the mass of phosphorylated hydroxypropyl methylcellulose.

[0016] Preferably, in step (4), the reaction temperature is 70-100°C and the reaction time is 2-7 h.

[0017] Preferably, in step (5), the agricultural solid waste is a mixture of livestock manure and plant straws with a mass ratio of 2-4:1; the mass ratio of the agricultural solid waste to the phosphorylated hydroxypropyl methylcellulose composite active bacterial residue is 2-5:1.

[0018] Preferably, in step (5), there is no oxygen explosion and no turning during anaerobic composting, and the anaerobic composting time is 5-10 days.

[0019] Preferably, in step (5), continuous oxygen explosion occurs during aerobic composting, the aeration rate is 0.1-1 L / min / kg, the aeration frequency is 2-10 min / h, turning is carried out every 12 h, and the composting time is 2-5 days.

[0020] Preferably, in step (5), the aerobic bacteria are Burkholderia vietnamiensis, the effective viable bacteria count ≥ 2×10 9 cfu / g, and the addition amount is 1.7%-4.3% of the phosphorylated hydroxypropyl methylcellulose composite active bacterial residue.

[0021] The beneficial effects of the present invention are as follows: 1. The present invention uses tylosin bacterial residue to prepare organic fertilizer. After the tylosin bacterial residue is modified, it is first subjected to anaerobic fermentation treatment and then aerobic fermentation treatment. The finally prepared organic fertilizer not only has a significantly reduced content of the antibiotic tylosin, which can meet the industry requirements, but also can increase the soil organic matter content, improve the soil structure, increase the soil fertility, and is beneficial to the growth of plants.

[0022] 2. The modification process of the tylosin mycelial residue in the present invention includes: first, irradiating the fresh tylosin mycelial residue with electron beams to eliminate most of the antibiotics therein, then treating it with the coupling agent KH-550 to coat a large number of amino groups on the surface of the mycelial residue, and then carrying out phosphorylation binding with phosphorylated hydroxypropyl methylcellulose, and finally preparing the phosphorylated amide hydroxypropyl methylcellulose composite active mycelial residue.

[0023] 3. Composting the composite active mycelial residue prepared by the present invention with agricultural solid waste. The composting is carried out by first anaerobic composting and subsequent aerobic composting. Anaerobic composting can quickly reduce the volume of organic matter, and aerobic composting can further decompose the remaining organic matter to improve the stability and maturity of the compost. Detailed implementation mode

[0024] The technical solutions of the present invention are illustrated by specific specific examples below. It should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before and after the combined steps or the insertion of other method steps between these clearly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. Moreover, unless otherwise specified, the numbers of each method step are only convenient tools for identifying each method step, rather than limiting the arrangement order of each method step or the scope in which the present invention can be implemented. The change or adjustment of their relative relationship, without substantial change in technical content, should also be regarded as the scope in which the present invention can be implemented.

[0025] To better understand the above technical solutions, the exemplary embodiments of the present invention are described in more detail below. Although the exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided so that the present invention can be understood more thoroughly and the scope of the present invention can be fully conveyed to those skilled in the art.

[0026] The present invention is further described below in conjunction with the following embodiments.

[0027] Example 1 A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelial residue, comprising the following steps: (1) First, irradiate the tylosin mycelial residue with electron beams. The parameters of the electron beam irradiation include: the accelerator energy is 1.5 MeV, the beam current is 60 mA; the irradiation absorption dose is 30 kGy. The obtained mycelial residue is placed in an oven and dried until the water content is lower than 5%, and then ground and sieved through a 60-mesh sieve to obtain mycelial residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 60°C and the time is 6 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 40%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.3:15; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 20%, the concentration of the sodium hydroxide solution is 0.5 mol / L, and the pH of the system is adjusted to 4, and then starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether are added, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 2:1:0.05:20, and undergoing a cross-linking reaction at a temperature of 50°C for 2 hours. After the reaction is completed, rinse with pure water three times and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in dioxane, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and dioxane is 1:0.6:25, and after stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 5% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 80°C, the reaction time is 5 hours, after the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 3:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 3:1, and after adjusting the moisture content of the mixture to 55%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 7 days. After the treatment is completed, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are mixed in, and the effective live bacteria count is ≥2×10 9 cfu / g, the added amount is 2.8% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.5L / min / kg, the aeration frequency is 6min / h, the pile is turned every 12h, the composting time is 3 days, and finally organic fertilizer is obtained.

[0028] Example 2 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.4 MeV, beam current of 70 mA, and irradiation absorbed dose of 50 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 100-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 70°C and the time is 2 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 60%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.5:10; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 15%-25%, the concentration of the sodium hydroxide solution is 0.3 mol / L, and the pH of the system is adjusted to 4, and then starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether are added, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 1:1:0.08:30, and undergoing a cross-linking reaction at a temperature of 60°C for 1 hour. After the reaction is completed, rinse with pure water three times and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in dioxane, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and dioxane is 1:0.4:35, and after stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 7% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 90°C, the reaction time is 3 hours, and after the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 4:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 5:1, and after adjusting the water content of the mixture to 55%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 7 days. After the treatment is completed, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are mixed in, and the effective live bacteria count is ≥2×10 9 cfu / g, the added amount is 3.5% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.2L / min / kg, the aeration frequency is 3min / h, the pile is turned every 12h, the composting time is 4 days, and finally organic fertilizer is obtained.

[0029] Example 3 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.6 MeV, beam current of 65 mA, and irradiation absorbed dose of 40 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 100-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 50°C and the time is 10 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 60%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.3:10; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 20%, the concentration of the sodium hydroxide solution is 0.4 mol / L, and the pH of the system is adjusted to 4, and then starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether are added, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 2:1:0.06:15, and undergoing a cross-linking reaction at a temperature of 45°C for 2 hours. After the reaction is completed, rinse with pure water three times and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in dioxane, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and dioxane is 1:0.5:20, and after stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 4% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 80°C, the reaction time is 6 hours, after the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 3:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 4:1, and after adjusting the moisture content of the mixture to 55%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 7 days. After the treatment is completed, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are mixed in, and the effective live bacteria count is ≥2×10 9cfu / g, the added amount is 2.2% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.6L / min / kg, the aeration frequency is 3min / h, the pile is turned every 12h, the composting time is 3 days, and finally organic fertilizer is obtained.

[0030] Example 4 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.2 MeV, beam current of 50 mA, and irradiation absorbed dose of 10 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 50-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 50°C and the time is 2 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 20%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.1:10; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 15%, the concentration of the sodium hydroxide solution is 0.1 mol / L, and the pH of the system is adjusted to 3.5, and then adding starch and hydroxypropyl methylcellulose, as well as 1,4-butanediol diglycidyl ether, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 1:1:0.02:10, and undergoing a cross-linking reaction at a temperature of 40°C for 1 hour. After the reaction is completed, rinsing with pure water three times and drying to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in tetrahydrofuran, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and tetrahydrofuran is 1:0.4:15, stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 3% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 70°C, the reaction time is 2 hours, after the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 2:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 2:1, and after adjusting the moisture content of the mixture to 50%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 5 days. After the treatment is completed, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are mixed in, and the effective live bacteria count is ≥2×10 9 cfu / g, the added amount is 1.7% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.1L / min / kg, the aeration frequency is 2min / h, the pile is turned every 12h, the composting time is 2 days, and finally organic fertilizer is obtained.

[0031] Example 5 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.8 MeV, beam current of 70 mA, and irradiation absorbed dose of 50 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 100-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 70°C and the time is 10 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 60%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.5:20; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 25%, the concentration of the sodium hydroxide solution is 1 mol / L, and the pH of the system is adjusted to 4.5, and then adding starch and hydroxypropyl methylcellulose, as well as 1,4-butanediol diglycidyl ether, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 3:1:0.08:30, and undergoing a cross-linking reaction at a temperature of 60°C for 3 hours. After the reaction is completed, rinsing with pure water three times and drying to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in chloroform, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and chloroform is 1:0.8:35, and after stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 8% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 100° C., and the reaction time is 7 hours. After the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 4:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 5:1, and after adjusting the moisture content of the mixture to 60%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 10 days. After the treatment, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are added, and the effective live bacteria count is ≥2×10 9 cfu / g, the added amount is 4.3% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 1L / min / kg, the aeration frequency is 10min / h, the pile is turned every 12h, the composting time is 5 days, and finally organic fertilizer is obtained.

[0032] Example 6 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.3 MeV, beam current of 55 mA, and irradiation absorbed dose of 20 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 60-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 55°C and the time is 3 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 30%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.2:16; (3) Add sodium hydroxide solution dropwise to sodium dihydrogen phosphate solution. The mass fraction of sodium dihydrogen phosphate solution is 15%, and the concentration of sodium hydroxide solution is 0.2 mol / L. Adjust the pH of the system to 4.5, then add starch, hydroxypropyl methylcellulose, and 1,4-butanediol diglycidyl ether. The mass fractions of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether, and sodium dihydrogen phosphate solution are 1:1:0.03:20. After cross-linking reaction, the reaction temperature is 50 °C and the time is 2 h. After the reaction, rinse three times with pure water and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mix the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in dioxane. The mass ratio of aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose, and dioxane is 1:0.5:20. After stirring evenly, add aluminum chloride as a catalyst. The addition amount of aluminum chloride is 4% of the mass of phosphorylated hydroxypropyl methylcellulose. Heat up and carry out a stirring reaction. The reaction temperature is 80 °C and the reaction time is 4 h. After the reaction, remove the solvent under reduced pressure and dry to obtain phosphorylated hydroxypropyl methylcellulose composite active bacterial residue; (5) Thoroughly mix agricultural solid waste and phosphorylated hydroxypropyl methylcellulose composite active bacterial residue. The agricultural solid waste is a mixture of livestock manure and plant straw with a mass ratio of 4:1; the mass ratio of agricultural solid waste to phosphorylated hydroxypropyl methylcellulose composite active bacterial residue is 2:1. After adjusting the water content of the mixture to 50%, carry out anaerobic composting treatment. During anaerobic composting, there is no oxygen explosion and no turning of the pile. The anaerobic composting time is 5 days. After the treatment, mix in the aerobic bacterium Burkholderia vietnamiensis ATCC BAA-248, with an effective viable count ≥ 2×10 9 cfu / g, and the addition amount is 4.3% of the phosphorylated hydroxypropyl methylcellulose composite active bacterial residue. Carry out aerobic composting treatment. During aerobic composting, continuous oxygen explosion is carried out, the aeration rate is 0.2 L / min / kg, the aeration frequency is 3 min / h, and the pile is turned over every 12 h. The composting time is 5 days, and finally obtain organic fertilizer.

[0033] Example 7 A method for preparing organic fertilizer by anaerobic fermentation of tylosin bacterial residue, comprising the following steps: (1) First, perform electron beam irradiation treatment on tylosin bacterial residue. The parameters of electron beam irradiation include: accelerator energy is 1.7 MeV, beam current is 70 mA; irradiation absorption dose is 40 kGy. Place the obtained bacterial residue in an oven to dry until the water content is lower than 5%, then grind and pass through a 100-mesh sieve to obtain bacterial residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 70°C and the time is 4 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 30%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.4:15; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 15%-25%, the concentration of the sodium hydroxide solution is 0.3 mol / L, and the pH of the system is adjusted to 4, and then starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether are added, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 2:1:0.05:20, and undergoing a cross-linking reaction at a temperature of 55°C for 2 hours. After the reaction is completed, rinse with pure water three times and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) Mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in dioxane, wherein the mass ratio of the aminated bacterial residue, phosphorylated hydroxypropyl methylcellulose and dioxane is 1:0.5:30, and after stirring evenly, adding aluminum chloride as a catalyst, wherein the amount of aluminum chloride added is 4% of the mass of the phosphorylated hydroxypropyl methylcellulose, heating and stirring to react, the reaction temperature is 80°C, the reaction time is 3 hours, after the reaction is completed, removing the solvent under reduced pressure, and drying to obtain phosphoramidated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, wherein the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 2:1; the mass ratio of the agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 3:1, and after adjusting the moisture content of the mixture to 55%, anaerobic composting is performed, and no oxygen explosion and no turning of the compost are performed during the anaerobic composting. The anaerobic composting time is 5-10 days. After the treatment is completed, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are mixed in, and the effective live bacteria count is ≥2×10 9 cfu / g, the added amount is 3.6% of the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue, and aerobic composting is performed. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.2L / min / kg, the aeration frequency is 4min / h, the pile is turned every 12h, the composting time is 3 days, and finally organic fertilizer is obtained.

[0034] Comparative Example 1 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues is different from that of Example 1 in that the aminated residues prepared in Example 1 are used to replace the phosphoramidated hydroxypropyl methylcellulose composite active residues, and then composted with agricultural solid waste, and the remaining steps are the same as those of Example 1. Specifically: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.5 MeV, beam current of 60 mA, and irradiation absorbed dose of 30 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 60-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 60°C and the time is 6 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 40%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.3:15; (3) The agricultural solid waste and the amination bacterial residue are fully mixed. The agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 3:1. The mass ratio of agricultural solid waste and amination bacterial residue is 3:1. After adjusting the water content of the mixture to 55%, anaerobic composting is performed. During the anaerobic composting, no oxygen explosion and no turning of the compost are performed. The anaerobic composting time is 7 days. After the treatment, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are added, and the effective viable bacteria count is ≥ 2×10 9 cfu / g, the added amount is 2.8% of the amination bacterial residue, and aerobic composting is used. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.5L / min / kg, the aeration frequency is 6min / h, the pile is turned every 12h, the composting time is 3 days, and finally organic fertilizer is obtained.

[0035] Comparative Example 2 A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues is different from Example 1 in that the aminated residues prepared in Example 1 and phosphorylated hydroxypropyl methylcellulose are used to replace the phosphoramidated hydroxypropyl methylcellulose composite active residues, and then composted with agricultural solid waste, and the remaining steps are the same as Example 1. Specifically: A method for preparing organic fertilizer by anaerobic fermentation of tylosin residues comprises the following steps: (1) The tylosin residue was first subjected to electron beam irradiation treatment, and the parameters of the electron beam irradiation included: accelerator energy of 1.5 MeV, beam current of 60 mA, and irradiation absorbed dose of 30 kGy. The obtained residue was placed in an oven for drying until the water content was less than 5%, and then ground and passed through a 60-mesh sieve to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, add the coupling agent KH-550 after it is fully dispersed, heat it to reflux, and then keep it warm. The temperature of the warm treatment is 60°C and the time is 6 hours. After the reaction is completed, filter, wash and dry to obtain the amino fungus residue; wherein the mass fraction of the ethanol solution is 40%, and the mass ratio of the fungus residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.3:15; (3) Adding sodium hydroxide solution dropwise into the sodium dihydrogen phosphate solution, the mass fraction of the sodium dihydrogen phosphate solution is 20%, the concentration of the sodium hydroxide solution is 0.5 mol / L, and the pH of the system is adjusted to 4, and then starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether are added, the mass fraction of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution is 2:1:0.05:20, and undergoing a cross-linking reaction at a temperature of 50°C for 2 hours. After the reaction is completed, rinse with pure water three times and dry to prepare phosphorylated hydroxypropyl methylcellulose; (4) The agricultural solid waste, aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose are fully mixed. The agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 3:1. The mass ratio of agricultural solid waste, aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose is 3:0.63:0.37. After adjusting the moisture content of the mixture to 55%, anaerobic composting is performed. During the anaerobic composting, no oxygen explosion and no turning of the compost are performed. The anaerobic composting time is 7 days. After the treatment, aerobic bacteria Burkholderia vietnamese ATCC BAA-248 are added, and the effective viable count is ≥2×10 9 cfu / g, the added amount is 2.8% of the amination bacterial residue, and aerobic composting is used. During aerobic composting, oxygen is continuously exploded, the aeration volume is 0.5L / min / kg, the aeration frequency is 6min / h, the pile is turned every 12h, the composting time is 3 days, and finally organic fertilizer is obtained.

[0036] Experimental testing The organic fertilizers of Example 1 and Comparative Examples 1-2 were specifically applied to rapeseed cultivation in a certain place in Jiangsu Province, and the variety was Huaiyou No. 18. Sowing was carried out on September 16, 2023, deep plowing and sun-cutting were carried out 3 times before sowing, and rapeseed seedlings (4-5 true leaves were fixed) were transplanted into the land, and seedlings were thinned in time after the seedlings were all grown. The transplanting row and plant spacing were 0.5×0.15 meters, and fertilization was started 7 days after normal watering, with a fertilizer amount of 8kg / mu, and then 6kg / mu was applied on December 15, 2023. Sclerotinia disease was controlled twice during the flowering period, and aphids were controlled in time until harvesting on May 12, 2024.

[0037] Among them, the tylosin mycelium residue comes from Jiangsu Huiju Pharmaceutical Co., Ltd., with an initial tylosin content of 0.72 wt%. It is provided through cold-chain transportation and stored at 4°C before use. The tylosin content (%) = (the mass of tylosin in the tylosin mycelium residue organic fertilizer / the mass of tylosin in the tylosin mycelium residue before treatment) * 100%.

[0038] After measuring the corresponding indicators, the results are shown in Table 1: Table 1 Comparison of the results of different fertilizers

[0039] As can be seen from Table 1, when the organic fertilizer prepared in Example 1 of the present invention is used in the cultivation of rapeseed, compared with Comparative Examples 1-2, the yield is higher, and the elimination rate of tylosin in the tylosin mycelium residue is also higher.

[0040] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing organic fertilizer by anaerobic fermentation of tylosin bacterial residue, characterized in that, The following steps are involved: (1) The tylosin residue is first subjected to electron beam irradiation treatment, the obtained residue is placed in an oven for drying, and then ground and sieved to obtain residue powder; (2) Put the fungus residue powder into an ethanol solution, and after it is fully dispersed, add the coupling agent KH-550, raise the temperature to reflux, and then keep it warm. After the reaction is completed, filter, wash and dry to obtain the amination fungus residue; (3) adding sodium hydroxide solution dropwise to the sodium dihydrogen phosphate solution to adjust the pH of the system to 3.5-4.5, then adding starch and hydroxypropyl methylcellulose and 1,4-butanediol diglycidyl ether, and performing a cross-linking reaction. After the reaction is completed, washing with pure water three times and drying to prepare phosphorylated hydroxypropyl methylcellulose; (4) mixing the aminated bacterial residue and phosphorylated hydroxypropyl methylcellulose in an organic solvent, stirring evenly, adding aluminum chloride as a catalyst, heating and stirring to react, and after the reaction is completed, removing the solvent under reduced pressure and drying to obtain phosphorylated hydroxypropyl methylcellulose composite active bacterial residue; (5) The agricultural solid waste and the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue are fully mixed, and the water content of the mixture is adjusted to 50%-60%, and then anaerobic composting is performed. After the treatment, aerobic bacteria are added and aerobic composting is performed to finally obtain organic fertilizer.

2. The method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (1), the parameters of electron beam irradiation include: accelerator energy of 1.2-1.8 MeV, beam current of 50-70 mA; and irradiation absorbed dose of 10-50 kGy.

3. A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (1), drying is performed in an oven until the moisture content is less than 5%; the temperature in the oven is 50-80° C., and the mesh size of the sieve is 50-100 mesh.

4. A method for preparing organic fertilizer by anaerobic fermentation of tylosin bacterial residue according to claim 1, characterized in that In step (2), the mass fraction of the ethanol solution is 20%-60%, and the mass ratio of the mushroom residue powder, the coupling agent KH-550 and the ethanol solution is 1:0.1-0.5:10-20.

5. A method for preparing organic fertilizer by anaerobic fermentation of tylosin bacterial residue according to claim 1, characterized in that, In step (3), the mass fractions of starch, hydroxypropyl methylcellulose, 1,4-butanediol diglycidyl ether and sodium dihydrogen phosphate solution are 1-3:1:0.02-0.08:10-30.

6. A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (3), the mass fraction of the sodium dihydrogen phosphate solution is 15%-25%, and the concentration of the sodium hydroxide solution is 0.1-1 mol / L; the temperature of the cross-linking reaction is 40-60° C., and the time is 1-3 h.

7. A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (4), the mass ratio of the amination bacterial residue, the phosphorylated hydroxypropyl methylcellulose and the organic solvent is 1:0.4-0.8:15-35.

8. A method for preparing organic fertilizer by anaerobic fermentation of tylosin bacterial residue according to claim 1, characterized in that, In step (4), the amount of aluminum chloride added is 3%-8% of the mass of phosphorylated hydroxypropyl methylcellulose; the reaction temperature is 70-100°C, and the reaction time is 2-7h.

9. A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (5), the agricultural solid waste is a mixture of livestock manure and plant straw in a mass ratio of 2-4:1; the mass ratio of the agricultural solid waste to the phosphoamidated hydroxypropyl methylcellulose composite active bacterial residue is 2-5:

1.

10. A method for preparing organic fertilizer by anaerobic fermentation of tylosin mycelium residue according to claim 1, characterized in that, In step (5), there is no oxygen explosion and no turning of the pile during anaerobic composting, and the anaerobic composting time is 5 - 10 days; during aerobic composting, oxygen is continuously exploded, the aeration volume is 0.1 - 1 L / min / kg, the aeration frequency is 2 - 10 min / h, the pile is turned once every 12 h, and the composting time is 2 - 5 days.

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