Process for preparing organic fertilizer from tylosin residues

Abstract

The invention discloses a process for preparing an organic fertilizer from tylosin residues, and relates to the technical field of organic fertilizers. When the organic fertilizer is prepared from the tylosin fungus residues, firstly, modified carboxymethyl cellulose and hydrogen peroxide are used for pretreating the tylosin fungus residues, then, the pretreated tylosin fungus residues and auxiliary materials are mixed and then subjected to aerobic composting fermentation, drying, smashing and pelleting, and the organic fertilizer is prepared. The modified carboxymethyl cellulose is obtained by co-precipitating sodium carboxymethyl cellulose and an iron ion solution and then reacting with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride. According to the process for preparing the organic fertilizer from the tylosin fungus residues, the tylosin removal efficiency is high, the treatment time is short, and reduction, harmlessness and recycling of the tylosin fungus residues are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of organic fertilizers, in particular to a process for preparing organic fertilizers from tylosin residues. Background Art

[0002] The use of antibiotics has remained high, especially in animal husbandry and aquaculture, where they are used in large quantities to prevent and treat animal diseases and promote growth. However, this widespread use has also brought serious problems, one of which is the production of a large amount of antibiotic residues. These residues are waste generated during the production of antibiotics, containing incompletely separated antibiotics, culture medium residues, and other organic matter. With the increase in the use of antibiotics, the amount of residues has also increased dramatically, and how to reasonably handle and utilize these residues has become an urgent problem to be solved.

[0003] Tylosin is a macrolide antibiotic widely used in animal husbandry, mainly for the treatment of respiratory diseases and intestinal infections in poultry and livestock. In the process of producing tylosin, a large amount of bacterial residue is also produced. These tylosin bacterial residues not only contain incompletely extracted tylosin, but are also rich in organic matter and have the value of fertilizer utilization.

[0004] However, there are many problems in directly using tylosin residue to prepare organic fertilizer. Due to the high level of antibiotic residue in the residue, direct application may cause pollution to soil and plants, affecting the quality and safety of agricultural products. In addition, antibiotic residues may also be transmitted to humans through the food chain, posing a potential threat to human health. At the same time, the direct use of antibiotic residues may also cause microbial resistance problems, further exacerbating the spread and diffusion of antibiotic resistance. Therefore, before using tylosin residue to prepare organic fertilizer, effective measures must be taken to remove the antibiotic residues to ensure the safety and effectiveness of organic fertilizer. Summary of the invention

[0005] The purpose of the present invention is to provide a process for preparing organic fertilizer from tylosin residue to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: A process for preparing organic fertilizer from tylosin residues comprises the following preparation steps: (1) ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water are mixed in a mass ratio of 1:2.6:100, heated to 90°C and stirred for 5-10 minutes under nitrogen protection, and then sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10-11 times that of ferrous chloride tetrahydrate are added, reacted for 30 minutes, cooled to room temperature, separated by a magnet, and washed with pure water for 3-4 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water are mixed in a mass ratio of 1:(12-15):0.5, and a 0.37 g / L sodium hydroxide solution in an amount of 12-15 times the mass of the modified carboxymethyl cellulose is added. After reacting for 30 minutes, the mixture is heated to 50-60°C, and 0.1-0.3 times the mass of the modified carboxymethyl cellulose is added with 3-chloro-2-hydroxypropyltrimethylammonium chloride. The mixture is reacted for 2-3 hours. After the reaction is completed, the mixture is cooled to room temperature, evaporated under reduced pressure, and dried in a vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue are mixed in a mass ratio of 1:(20-30):(2-3), reacted at 95-110°C for 60-90 minutes under sealed conditions, and after the reaction is completed, separated by a magnet, the filtrate is retained by solid-liquid separation, and vacuum dried to obtain the pre-treated residue; (4) The pretreated fungus residue and auxiliary materials are mixed in a mass ratio of 1:(2-4), and then aerobic composting and fermentation are performed, followed by drying, crushing and granulation to obtain organic fertilizer.

[0007] As an optimization, the sodium carboxymethyl cellulose solution in step (1) is obtained by mixing sodium carboxymethyl cellulose and pure water in a mass ratio of 1:50, the mass of sodium carboxymethyl cellulose is 0.15-0.25 times that of ferrous chloride tetrahydrate, and the relative molecular weight of sodium carboxymethyl cellulose is 7.8*10 3 , the degree of substitution is 1.

[0008] As an optimization, the moisture content of the tylosin residue in step (3) is 65%-80%, and the concentration is 1400-1600 mg / kg.

[0009] As an optimization, the auxiliary material in step (4) is one or more of corn cobs, wheat straw, and sawdust, and the moisture content of the auxiliary material is 8%-12%.

[0010] As an optimization, the aerobic composting fermentation process in step (4) is as follows: after the compost temperature rises to 55-65°C, keep warm for 3-4 days, turn the compost over once every 3-4 days, ferment for 15-17 days, cool to 30-40°C, and ferment for 3-5 days.

[0011] Compared with the prior art, the beneficial effects achieved by the present invention are: When the tylosin residue is used to prepare the organic fertilizer, the modified carboxymethyl cellulose and hydrogen peroxide are firstly used to pretreat the tylosin residue, and then the pretreated tylosin residue and auxiliary materials are mixed, aerobic composting and fermentation are performed, and then the organic fertilizer is dried, crushed and granulated; the modified carboxymethyl cellulose is obtained by reacting sodium carboxymethyl cellulose and an iron ion solution with 3-chloro-2-hydroxypropyltrimethylammonium chloride after coprecipitation.

[0012] Firstly, sodium carboxymethyl cellulose and an iron ion solution are coprecipitated to obtain carboxymethyl cellulose containing magnetic ferroferric oxide, and then the carboxymethyl cellulose and 3-chloro-2-hydroxypropyltrimethylammonium chloride are reacted to obtain modified carboxymethyl cellulose containing quaternary ammonium salt; the antibiotic residue in the tylosin bacterial residue is relatively high, and there are also some bacterial species residues, which will affect the subsequent fermentation process and may also cause pollution to soil and plants; the material obtained by coprecipitating sodium carboxymethyl cellulose and an iron ion solution is a Fenton catalyst, which can catalyze hydrogen peroxide to produce free radicals to degrade the tylosin remaining in the bacterial residue; the grafting of the quaternary ammonium salt has a good antibacterial effect; in the process of the catalyst degrading tylosin, the cellulose on the surface of the magnetic ferroferric oxide will be degraded to a certain extent; the degradation of the cellulose can also provide components for subsequent fertilizers; and the magnetic ferroferric oxide can be separated by a magnet, so the addition of the carboxymethyl cellulose containing the magnetic ferroferric oxide will not affect the subsequent process; and the preparation process of the invention can efficiently remove the tylosin remaining in the bacterial residue. DETAILED DESCRIPTION

[0013] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0014] The tylosin residue used in the following examples and comparative examples has a water content of 74% and a concentration of 1459.6 mg / kg;

[0015] Embodiment 1: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.15 times that of ferrous chloride tetrahydrate, and the relative molecular weight of which is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 10 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:12:0.5, and a 0.37 g / L sodium hydroxide solution (12 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 minutes, the temperature was raised to 50°C, and 0.1 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride. The mixture was reacted for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried in vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:20:2, and reacted at 110°C for 90 minutes under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (4) The pretreated fungus residue and wheat straw (water content 12%) were mixed in a mass ratio of 1:2 and aerobic composting fermentation was performed. After the compost temperature rose to 65°C, it was kept warm for 4 days and then turned over once every 4 days. The compost was fermented for 17 days and then cooled to 40°C for 5 days. After fermentation, it was dried, crushed and granulated to obtain organic fertilizer.

[0016] Embodiment 2: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.21 times that of ferrous chloride tetrahydrate, and the relative molecular weight of which is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 7 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10.5 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:13:0.5, and a 0.37 g / L sodium hydroxide solution (13 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 minutes, the temperature was raised to 55°C, and 0.2 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride (2-hydroxypropyltrimethylammonium chloride). The reaction was continued for 2.5 hours. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried in vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:25:2.5, and reacted at 100°C for 70 minutes under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (4) Pretreated fungus residue, corn cobs (water content 11%), wheat straw and sawdust were mixed in a mass ratio of 1:2.3 and aerobic composting fermentation was performed. After the compost temperature rose to 60°C, it was kept warm for 3 days and then turned over once every 4 days. The compost was fermented for 16 days and then cooled to 35°C for 4 days. After fermentation, it was dried, crushed and granulated to obtain organic fertilizer.

[0017] Embodiment 3: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.25 times that of ferrous chloride tetrahydrate, and the relative molecular weight of which is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 5 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 11 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:15:0.5, and a 0.37 g / L sodium hydroxide solution (15 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 minutes, the temperature was raised to 50°C, and 0.3 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride (2-hydroxypropyltrimethylammonium chloride). The mixture was reacted for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried in vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:30:3, and reacted at 95°C for 60 minutes under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (4) Pretreated fungus residue and sawdust (water content 12%) were mixed in a mass ratio of 1:4 and then aerobic composting fermentation was performed. After the compost temperature rose to 55°C, it was kept warm for 3 days and then turned over once every 3 days. After fermentation for 15 days, the temperature was lowered to 30°C and the fermentation time was 3 days. After fermentation, it was dried, crushed and granulated to obtain organic fertilizer.

[0018] Example 4 A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.23 times that of ferrous chloride tetrahydrate, and the relative molecular weight of which is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 6 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10.7 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:14.6:0.5, and a 0.37 g / L sodium hydroxide solution (14.7 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 min, the temperature was raised to 58 ° C, and 0.27 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride. The reaction was continued for 2.7 h. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and vacuum dried to obtain modified carboxymethyl cellulose; (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:28:2.6, and reacted at 106°C for 85 min under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (4) The pretreated fungus residue and auxiliary materials are mixed in a mass ratio of 1:3.7 and then aerobic composting fermentation is performed. After the compost temperature rises to 63°C, it is kept warm for 4 days and then turned over once every 4 days. The compost is fermented for 17 days and then cooled to 30°C for 5 days. After the fermentation is completed, it is dried, crushed and granulated to obtain organic fertilizer.

[0019] Embodiment 5: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.16 times that of ferrous chloride tetrahydrate. The relative molecular weight of sodium carboxymethyl cellulose is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 6 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10.2 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:12.5:0.5, and a 0.37 g / L sodium hydroxide solution (12.6 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 minutes, the temperature was raised to 52°C, and 0.14 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride (2-hydroxypropyltrimethylammonium chloride). The mixture was reacted for 2.3 hours. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and vacuum dried to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:22:2.3, and reacted at 97°C for 65 min under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (4) The pretreated fungus residue and auxiliary materials are mixed in a mass ratio of 1:2.3 and then aerobic composting fermentation is performed. After the compost temperature rises to 57°C, it is kept warm for 3 days and then turned over once every 3 days. The compost is fermented for 15 days and then cooled to 40°C for 5 days. After the fermentation is completed, it is dried, crushed and granulated to obtain organic fertilizer.

[0020] Comparative Example 1: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) The relative molecular weight of sodium carboxymethyl cellulose is 7.8*10 3 , the degree of substitution is 1; carboxymethyl cellulose, isopropanol and pure water are mixed in a mass ratio of 1:13:0.5, 0.37 g / L sodium hydroxide solution of 13 times the mass of modified carboxymethyl cellulose is added, react for 30 minutes, heat to 55°C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride of 0.2 times the mass of modified carboxymethyl cellulose, react for 2.5 hours, cool to room temperature after the reaction is completed, evaporate under reduced pressure, and vacuum dry to obtain modified carboxymethyl cellulose; (2) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue were mixed in a mass ratio of 1:25:2.5, and reacted at 100°C for 70 minutes under sealed conditions. After the reaction, the mixture was separated by a magnet, the filtrate was retained by solid-liquid separation, and the pre-treated residue was obtained by vacuum drying; (3) Pretreated fungus residue, corn cobs (water content 11%), wheat straw and sawdust were mixed in a mass ratio of 1:2.3 and aerobic composting fermentation was performed. After the compost temperature rose to 60°C, it was kept warm for 3 days and then turned over once every 4 days. The compost was fermented for 16 days and then cooled to 35°C for 4 days. After fermentation, it was dried, crushed and granulated to obtain organic fertilizer.

[0021] Comparative Example 2: A process for preparing organic fertilizer from tylosin bacteria residue, the process for preparing organic fertilizer from tylosin bacteria residue comprising the following preparation steps: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100, weigh sodium carboxymethyl cellulose, the mass of which is 0.21 times that of ferrous chloride tetrahydrate, and the relative molecular weight of which is 7.8*10 3 , the degree of substitution is 1; sodium carboxymethyl cellulose and pure water are mixed in a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution, and the mixture is heated to 90°C and stirred for 7 minutes under nitrogen protection, and then the sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10.5 times that of ferrous chloride tetrahydrate are added, and the mixture is reacted for 30 minutes and then cooled to room temperature, separated by a magnet, and washed with pure water for 3 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water were mixed in a mass ratio of 1:13:0.5, and a 0.37 g / L sodium hydroxide solution (13 times the mass of the modified carboxymethyl cellulose) was added. After reacting for 30 minutes, the temperature was raised to 55°C, and 0.2 times the mass of the modified carboxymethyl cellulose was added with 3-chloro-2-hydroxypropyltrimethylammonium chloride (2-hydroxypropyltrimethylammonium chloride). The reaction was continued for 2.5 hours. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried in vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose and tylosin residue were mixed in a mass ratio of 1:2.5, reacted at 100°C for 70 min under sealed conditions, and after the reaction, separated by magnet, the filtrate was retained by solid-liquid separation, and vacuum dried to obtain the pre-treated residue; (4) Pretreated fungus residue, corn cobs (water content 11%), wheat straw and sawdust were mixed in a mass ratio of 1:2.3 and aerobic composting fermentation was performed. After the compost temperature rose to 60°C, it was kept warm for 3 days and then turned over once every 4 days. The compost was fermented for 16 days and then cooled to 35°C for 4 days. After fermentation, it was dried, crushed and granulated to obtain organic fertilizer.

[0022] Test Example 1: The content of tylosin in the organic fertilizers prepared in the examples and comparative examples was tested by high performance liquid chromatography, and the removal rate of tylosin was calculated. The results are shown in Table 1.

[0023] Table 1

[0024] From the comparison of the experimental data of Examples 1 to 5 and Comparative Examples 1 to 2 in Table 1, it can be found that the organic fertilizer prepared by the present invention has a good tylosin removal rate.

[0025] By comparison, the tylosin removal rates of Examples 1 to 5 are greater than those of Comparative Examples 1 to 2, indicating that, first, carboxymethyl cellulose containing magnetic ferrosoferric oxide is obtained by coprecipitating sodium carboxymethyl cellulose and iron ion solution, and then carboxymethyl cellulose and 3-chloro-2-hydroxypropyltrimethylammonium chloride are reacted to obtain modified carboxymethyl cellulose containing quaternary ammonium salt; the antibiotic residue in the tylosin residue is relatively high, and there are also some bacterial residues, which will affect the subsequent fermentation process and may also cause pollution to the soil and plants; sodium carboxymethyl cellulose and iron ion solution are coprecipitated to obtain magnetic ferrosoferric oxide; and the quaternary ammonium salt is obtained by reacting carboxymethyl cellulose and 3-chloro-2-hydroxypropyltrimethylammonium chloride to obtain modified carboxymethyl cellulose containing quaternary ammonium salt. The material obtained after precipitation is a Fenton-type catalyst, which can catalyze hydrogen peroxide to generate free radicals to degrade the tylosin remaining in the mushroom residue. The grafting of quaternary ammonium salt has a good antibacterial effect. In the process of the catalyst degrading tylosin, the cellulose on the surface of the magnetic ferroferric oxide will be degraded to a certain extent. The degradation of cellulose can also provide components for subsequent fertilizers. The magnetic ferroferric oxide can be separated by a magnet, so the addition of the carboxymethyl cellulose of the magnetic ferroferric oxide will not affect the subsequent process. The preparation process of the invention can effectively remove the tylosin remaining in the mushroom residue.

[0026] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A process for preparing organic fertilizer from tylosin bacteria residue, characterized in that, The method comprises the following preparation steps: (1) ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water are mixed in a mass ratio of 1:2.6:100, heated to 90°C and stirred for 5-10 minutes under nitrogen protection, and then sodium carboxymethyl cellulose solution and 25wt% ammonia water with a mass of 10-11 times that of ferrous chloride tetrahydrate are added, reacted for 30 minutes, cooled to room temperature, separated by a magnet, and washed with pure water for 3-4 times to obtain pre-modified carboxymethyl cellulose; (2) Pre-modified carboxymethyl cellulose, isopropanol and pure water are mixed in a mass ratio of 1:(12-15):0.5, and a 0.37 g / L sodium hydroxide solution in an amount of 12-15 times the mass of the modified carboxymethyl cellulose is added. After reacting for 30 minutes, the mixture is heated to 50-60°C, and 0.1-0.3 times the mass of the modified carboxymethyl cellulose is added with 3-chloro-2-hydroxypropyltrimethylammonium chloride. The mixture is reacted for 2-3 hours. After the reaction is completed, the mixture is cooled to room temperature, evaporated under reduced pressure, and dried in a vacuum to obtain modified carboxymethyl cellulose. (3) pre-modified carboxymethyl cellulose, hydrogen peroxide, and tylosin residue are mixed in a mass ratio of 1:(20-30):(2-3), reacted at 95-110°C for 60-90 minutes under sealed conditions, and after the reaction is completed, separated by a magnet, the filtrate is retained by solid-liquid separation, and vacuum dried to obtain the pre-treated residue; (4) The pretreated fungus residue and auxiliary materials are mixed in a mass ratio of 1:(2-4), and then aerobic composting and fermentation are performed, followed by drying, crushing and granulation to obtain organic fertilizer.

2. a process for preparing organic fertilizer from tylosin bacteria residue according to claim 1, characterized in that, The sodium carboxymethyl cellulose solution in step (1) is obtained by mixing sodium carboxymethyl cellulose and pure water in a mass ratio of 1:50, the mass of sodium carboxymethyl cellulose is 0.15-0.25 times that of ferrous chloride tetrahydrate, and the relative molecular weight of sodium carboxymethyl cellulose is 7.8*10 3 , the degree of substitution is 1.

3. a process for preparing organic fertilizer from tylosin bacteria residue according to claim 1, characterized in that, The tylosin residue in step (3) has a water content of 65%-80% and a concentration of 1400-1600 mg / kg.

4. a kind of tylosin bacteria residue preparation process for organic fertilizer according to claim 1, is characterized in that, The auxiliary material in step (4) is one or more of corn cobs, wheat straws, and sawdust, and the moisture content of the auxiliary material is 8%-12%.

5. a kind of tylosin bacteria residue preparation process for organic fertilizer according to claim 1, is characterized in that, The aerobic composting fermentation process in step (4) is as follows: after the compost temperature rises to 55-65°C, it is kept warm for 3-4 days, and then the compost is turned over once every 3-4 days, fermented for 15-17 days, cooled to 30-40°C, and fermented for 3-5 days.

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