Process for preparing organic fertilizer from tylosin dregs

Abstract

This invention discloses a process for preparing organic fertilizer from tylosin bacterial residue, relating to the field of organic fertilizer technology. In this invention, the tylosin bacterial residue is first pretreated with modified carboxymethyl cellulose and hydrogen peroxide. Then, the pretreated residue is mixed with auxiliary materials, aerobic composted, dried, pulverized, and granulated to obtain organic fertilizer. The modified carboxymethyl cellulose is obtained by co-precipitating sodium carboxymethyl cellulose and iron ion solution, followed by reaction with 3-chloro-2-hydroxypropyltrimethylammonium chloride. This invention's process for preparing organic fertilizer from tylosin bacterial residue achieves high tylosin removal efficiency and short processing time, realizing the reduction, harmlessness, and resource utilization of tylosin bacterial residue.

Description

Technical Field

[0001] This invention relates to the field of organic fertilizer technology, specifically to a process for preparing organic fertilizer from tylosin bacterial residue. Background Technology

[0002] The use of antibiotics remains high, especially in animal husbandry and aquaculture, where they are used extensively to prevent and treat animal diseases and promote growth. However, this widespread use has also brought serious problems, one of which is the generation of large quantities of antibiotic residues. These residues are waste products generated during antibiotic production and contain incompletely separated antibiotics, culture medium residues, and other organic matter. With the increasing use of antibiotics, the amount of these residues is also rising sharply, making the rational treatment and utilization of them an urgent problem to be solved.

[0003] Tylosin is a macrolide antibiotic widely used in animal husbandry, primarily for treating respiratory and intestinal infections in poultry and livestock. The production of tylosin also generates a large amount of bacterial residue. This residue contains not only incompletely extracted tylosin but is also rich in organic matter, making it valuable for fertilizer use.

[0004] However, directly using tylosin-containing bacterial residue to prepare organic fertilizer presents numerous problems. Due to the high antibiotic residue levels, direct application may pollute the soil and plants, affecting the quality and safety of agricultural products. Furthermore, antibiotic residues may be transmitted to humans through the food chain, posing a potential threat to human health. Simultaneously, the direct use of antibiotic-containing bacterial residue may also trigger microbial resistance, further exacerbating the spread of antibiotic resistance. Therefore, before using tylosin-containing bacterial residue to prepare organic fertilizer, effective measures must be taken to remove antibiotic residues to ensure the safety and effectiveness of the organic fertilizer. Summary of the Invention

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

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A process for preparing organic fertilizer from tylosin inoculant residue includes the following preparation steps:

[0008] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:100. Under nitrogen protection, heat to 90℃ and stir for 5-10 min. Then add sodium carboxymethyl cellulose solution and 25wt% ammonia water at 10-11 times the mass of ferrous chloride tetrahydrate. After reacting for 30 min, cool to room temperature. After separation by magnet and washing with pure water 3-4 times, pre-modified carboxymethyl cellulose is obtained.

[0009] (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water at a mass ratio of 1:(12-15):0.5, add 0.37 g / L sodium hydroxide solution at 12-15 times the mass of modified carboxymethyl cellulose, react for 30 min, raise the temperature to 50-60℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride at 0.1-0.3 times the mass of modified carboxymethyl cellulose, react for 2-3 h, cool to room temperature after the reaction is completed, and obtain modified carboxymethyl cellulose by vacuum drying after rotary evaporation under reduced pressure.

[0010] (3) Mix the pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue at a mass ratio of 1:(20-30):(2-3), react under sealed conditions at 95-110℃ for 60-90 min, after the reaction is completed, separate by magnet, retain the filtrate after solid-liquid separation, and obtain the pretreated bacterial residue by vacuum drying;

[0011] (4) After mixing the pretreated bacterial residue and auxiliary materials at a mass ratio of 1:(2-4), the mixture is aerobic composted and fermented, then dried, crushed and granulated to obtain organic fertilizer.

[0012] As an optimization, the sodium carboxymethyl cellulose solution in step (1) is obtained by mixing sodium carboxymethyl cellulose and pure water at a mass ratio of 1:50, wherein 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.

[0013] As an optimization, the tylosin residue in step (3) has a water content of 65%-80% and a concentration of 1400-1600 mg / kg.

[0014] 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%.

[0015] As an optimization, the aerobic composting fermentation process in step (4) is as follows: after the composting temperature is raised to 55-65℃, it is kept warm for 3-4 days, and then the pile is turned over. The turning frequency is once every 3-4 days. The fermentation lasts for 15-17 days, and the temperature is lowered to 30-40℃. The fermentation time is 3-5 days.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0017] In preparing organic fertilizer using tylosin bacterial residue, the present invention first pretreats the tylosin bacterial residue with modified carboxymethyl cellulose and hydrogen peroxide. Then, the pretreated tylosin bacterial residue and auxiliary materials are mixed, and after aerobic composting and fermentation, the residue is dried, crushed and granulated to obtain organic fertilizer. The modified carboxymethyl cellulose is obtained by co-precipitating sodium carboxymethyl cellulose and iron ion solution and reacting it with 3-chloro-2-hydroxypropyltrimethylammonium chloride.

[0018] First, sodium carboxymethyl cellulose and an iron ion solution are co-precipitated to obtain carboxymethyl cellulose containing magnetic iron(III) oxide. Then, carboxymethyl cellulose is reacted with 3-chloro-2-hydroxypropyltrimethylammonium chloride to obtain modified carboxymethyl cellulose containing quaternary ammonium salt. Tylosin bacterial residue has a high antibiotic residue and may also contain some bacterial residues, which will affect the subsequent fermentation process and may also pollute the soil and plants. The material obtained by co-precipitating sodium carboxymethyl cellulose and an iron ion solution is a Fenton-type catalyst, which can catalyze hydrogen peroxide to generate free radicals, thereby degrading the residual tylosin in the bacterial residue. The grafting of quaternary ammonium salt has a good antibacterial effect. During the process of catalyst degradation of tylosin, the cellulose on the surface of magnetic iron(III) oxide will be degraded to a certain extent. The degradation of cellulose can also provide components for subsequent fertilizers. Since magnetic iron(III) oxide can be separated by a magnet, the addition of carboxymethyl cellulose containing magnetic iron(III) oxide will not affect the subsequent process. The preparation process of this invention can efficiently remove residual tylosin from bacterial residue. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] The tylosin residue used in the following examples and comparative examples had a moisture content of 74% and a concentration of 1459.6 mg / kg;

[0021] Example 1:

[0022] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0023] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose is 0.15 times that of ferrous chloride tetrahydrate. The relative molecular weight of sodium carboxymethyl cellulose is 7.8*10. 3The degree of substitution is 1. Sodium carboxymethyl cellulose and pure water are mixed at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 10 min. Then, sodium carboxymethyl cellulose solution and 25 wt% ammonia water (10 times the mass of ferrous chloride tetrahydrate) are added. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water three times, pre-modified carboxymethyl cellulose is obtained.

[0024] (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water in a mass ratio of 1:12:0.5, add 0.37 g / L sodium hydroxide solution at 12 times the mass of modified carboxymethyl cellulose, react for 30 min, heat to 50 °C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride at 0.1 times the mass of modified carboxymethyl cellulose, react for 3 h, cool to room temperature after the reaction is completed, and obtain modified carboxymethyl cellulose by vacuum drying after rotary evaporation under reduced pressure.

[0025] (3) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue were mixed at a mass ratio of 1:20:2 and reacted at 110°C for 90 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, and the filtrate was retained after solid-liquid separation and vacuum drying to obtain the pre-treated bacterial residue.

[0026] (4) The pretreated bacterial residue and wheat straw (moisture content 12%) are mixed at a mass ratio of 1:2 and then aerobic composting is carried out. After the composting temperature is raised to 65℃, it is kept warm for 4 days and then turned over. The turning frequency is once every 4 days. The fermentation lasts for 17 days. The temperature is then lowered to 40℃ and the fermentation time is 5 days. After the fermentation is completed, the compost is dried, crushed and granulated to obtain organic fertilizer.

[0027] Example 2:

[0028] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0029] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose is 0.21 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 at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 7 min. Then, 25 wt% ammonia water with 10.5 times the mass of ferrous chloride tetrahydrate is added to the sodium carboxymethyl cellulose solution. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water 3 times, pre-modified carboxymethyl cellulose is obtained.

[0030] (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water in a mass ratio of 1:13:0.5, add 0.37 g / L sodium hydroxide solution (13 times the mass of modified carboxymethyl cellulose), react for 30 min, heat to 55 °C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride (0.2 times the mass of modified carboxymethyl cellulose), react for 2.5 h, cool to room temperature after reaction, evaporate under reduced pressure, and vacuum dry to obtain modified carboxymethyl cellulose;

[0031] (3) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue were mixed at a mass ratio of 1:25:2.5 and reacted at 100°C for 70 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, the solid and liquid were separated and the filtrate was retained and dried under vacuum to obtain the pre-treated bacterial residue.

[0032] (4) The pretreated bacterial residue, corn cob (moisture content 11%), wheat straw and sawdust are mixed in a mass ratio of 1:2.3 and then aerobic composting is carried out. After the composting temperature is raised to 60℃, it is kept warm for 3 days and then turned over. The turning frequency is once every 4 days. The fermentation lasts for 16 days. The temperature is then lowered to 35℃ and the fermentation time is 4 days. After the fermentation is completed, the compost is dried, crushed and granulated to obtain organic fertilizer.

[0033] Example 3:

[0034] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0035] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose is 0.25 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 at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 5 min. Then, sodium carboxymethyl cellulose solution and 25 wt% ammonia water (11 times the mass of ferrous chloride tetrahydrate) are added. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water three times, pre-modified carboxymethyl cellulose is obtained.

[0036] (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water in a mass ratio of 1:15:0.5, add 0.37 g / L sodium hydroxide solution at 15 times the mass of modified carboxymethyl cellulose, react for 30 min, heat to 50 °C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride at 0.3 times the mass of modified carboxymethyl cellulose, react for 2 h, cool to room temperature after the reaction is completed, and obtain modified carboxymethyl cellulose by vacuum drying after rotary evaporation under reduced pressure.

[0037] (3) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue were mixed at a mass ratio of 1:30:3 and reacted at 95°C for 60 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, and the filtrate was retained after solid-liquid separation and vacuum drying to obtain the pre-treated bacterial residue.

[0038] (4) The pretreated bacterial residue and sawdust (moisture content 12%) are mixed at a mass ratio of 1:4 and then aerobic composting is carried out. After the composting temperature is raised to 55℃, it is kept warm for 3 days and then turned over. The turning frequency is once every 3 days. After 15 days of fermentation, the temperature is lowered to 30℃ and the fermentation time is 3 days. After the fermentation is completed, it is dried, crushed and granulated to obtain organic fertilizer.

[0039] Example 4

[0040] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0041] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose is 0.23 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 at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 6 min. Then, 25 wt% ammonia water with 10.7 times the mass of ferrous chloride tetrahydrate is added to the sodium carboxymethyl cellulose solution. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water 3 times, pre-modified carboxymethyl cellulose is obtained.

[0042] (2) Premodified carboxymethyl cellulose, isopropanol, and pure water were mixed in a mass ratio of 1:14.6:0.5. A 0.37 g / L sodium hydroxide solution with a mass of 14.7 times that of the modified carboxymethyl cellulose was added. After reacting for 30 min, the temperature was raised to 58 °C. 3-chloro-2-hydroxypropyltrimethylammonium chloride with a mass of 0.27 times that of the modified carboxymethyl cellulose was added. The reaction was carried out for 2.7 h. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried under vacuum to obtain modified carboxymethyl cellulose.

[0043] (3) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue were mixed at a mass ratio of 1:28:2.6 and reacted at 106℃ for 85 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, the solid and liquid were separated and the filtrate was retained and dried under vacuum to obtain the pre-treated bacterial residue.

[0044] (4) The pretreated bacterial residue and auxiliary materials are mixed at a mass ratio of 1:3.7 and then aerobic composting is carried out. After the composting temperature rises to 63℃, it is kept warm for 4 days and then turned over. The turning frequency is once every 4 days. The fermentation lasts for 17 days. The temperature is then lowered to 30℃ and the fermentation time is 5 days. After the fermentation is completed, the compost is dried, crushed and granulated to obtain organic fertilizer.

[0045] Example 5:

[0046] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0047] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose 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 at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 6 min. Then, 25 wt% ammonia water with 10.2 times the mass of ferrous chloride tetrahydrate is added to the sodium carboxymethyl cellulose solution. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water 3 times, pre-modified carboxymethyl cellulose is obtained.

[0048] (2) Premodified carboxymethyl cellulose, isopropanol, and pure water were mixed in a mass ratio of 1:12.5:0.5. A 0.37 g / L sodium hydroxide solution with a mass of 12.6 times that of the modified carboxymethyl cellulose was added. After reacting for 30 min, the temperature was raised to 52 °C. 3-chloro-2-hydroxypropyltrimethylammonium chloride with a mass of 0.14 times that of the modified carboxymethyl cellulose was added. The reaction was carried out for 2.3 h. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried under vacuum to obtain modified carboxymethyl cellulose.

[0049] (3) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial 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 was completed, the residue was separated by a magnet, and the filtrate was retained after solid-liquid separation and vacuum drying to obtain the pre-treated bacterial residue.

[0050] (4) The pretreated bacterial residue and auxiliary materials are mixed at a mass ratio of 1:2.3 and then aerobic composting is carried out. After the composting temperature rises to 57℃, it is kept warm for 3 days and then turned over. The turning frequency is once every 3 days. After 15 days of fermentation, the temperature is lowered to 40℃ and the fermentation time is 5 days. After the fermentation is completed, it is dried, crushed and granulated to obtain organic fertilizer.

[0051] Comparative Example 1:

[0052] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0053] (1) The relative molecular weight of sodium carboxymethyl cellulose is 7.8*10 3 The degree of substitution was 1. Carboxymethyl cellulose, isopropanol, and pure water were mixed in a mass ratio of 1:13:0.5. A 0.37 g / L sodium hydroxide solution with a mass of 13 times that of the modified carboxymethyl cellulose was added. After reacting for 30 min, the temperature was raised to 55 °C, and 3-chloro-2-hydroxypropyltrimethylammonium chloride with a mass of 0.2 times that of the modified carboxymethyl cellulose was added. The reaction was carried out for 2.5 h. After the reaction was completed, the mixture was cooled to room temperature, evaporated under reduced pressure, and dried under vacuum to obtain the modified carboxymethyl cellulose.

[0054] (2) The pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue were mixed at a mass ratio of 1:25:2.5 and reacted at 100°C for 70 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, and the filtrate was retained after solid-liquid separation and vacuum drying to obtain the pre-treated bacterial residue.

[0055] (3) The pretreated bacterial residue, corn cob (moisture content 11%), wheat straw and sawdust are mixed in a mass ratio of 1:2.3 and then aerobic composting is carried out. After the composting temperature is raised to 60℃, it is kept warm for 3 days and then turned over. The turning frequency is once every 4 days. The fermentation lasts for 16 days. The temperature is then lowered to 35℃ and the fermentation time is 4 days. After the fermentation is completed, the compost is dried, crushed and granulated to obtain organic fertilizer.

[0056] Comparative Example 2:

[0057] A process for preparing organic fertilizer from tylosin inoculant residue, comprising the following preparation steps:

[0058] (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate, and pure water in a mass ratio of 1:2.6:100. Weigh out sodium carboxymethyl cellulose. The mass of sodium carboxymethyl cellulose is 0.21 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 at a mass ratio of 1:50 to obtain a sodium carboxymethyl cellulose solution. Under nitrogen protection, the solution is heated to 90°C and stirred for 7 min. Then, 25 wt% ammonia water with 10.5 times the mass of ferrous chloride tetrahydrate is added to the sodium carboxymethyl cellulose solution. After reacting for 30 min, the solution is cooled to room temperature. After separation by magnet and washing with pure water 3 times, pre-modified carboxymethyl cellulose is obtained.

[0059] (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water in a mass ratio of 1:13:0.5, add 0.37 g / L sodium hydroxide solution (13 times the mass of modified carboxymethyl cellulose), react for 30 min, heat to 55 °C, add 3-chloro-2-hydroxypropyltrimethylammonium chloride (0.2 times the mass of modified carboxymethyl cellulose), react for 2.5 h, cool to room temperature after reaction, evaporate under reduced pressure, and vacuum dry to obtain modified carboxymethyl cellulose;

[0060] (3) The pre-modified carboxymethyl cellulose and tylosin bacterial residue were mixed at a mass ratio of 1:2.5 and reacted at 100°C for 70 min under sealed conditions. After the reaction was completed, the residue was separated by a magnet, and the filtrate was retained after solid-liquid separation and vacuum drying to obtain the pre-treated bacterial residue.

[0061] (4) The pretreated bacterial residue, corn cob (moisture content 11%), wheat straw and sawdust are mixed in a mass ratio of 1:2.3 and then aerobic composting is carried out. After the composting temperature is raised to 60℃, it is kept warm for 3 days and then turned over. The turning frequency is once every 4 days. The fermentation lasts for 16 days. The temperature is then lowered to 35℃ and the fermentation time is 4 days. After the fermentation is completed, the compost is dried, crushed and granulated to obtain organic fertilizer.

[0062] Test Example 1:

[0063] The tylosin content in the organic fertilizers prepared in the examples and comparative examples was tested using high performance liquid chromatography, and the tylosin removal rate was calculated. The results are shown in Table 1.

[0064] Table 1

[0065]

[0066] A comparison of the experimental data from Examples 1-5 and Comparative Examples 1-2 in Table 1 reveals that the organic fertilizer prepared by this invention has a good tylosin removal rate.

[0067] By comparison, the tylosin removal rate in Examples 1-5 was greater than that in Comparative Examples 1-2. This indicates that, firstly, carboxymethyl cellulose sodium and iron ion solution were co-precipitated to obtain carboxymethyl cellulose containing magnetic iron oxide, and then the carboxymethyl cellulose was reacted with 3-chloro-2-hydroxypropyltrimethylammonium chloride to obtain modified carboxymethyl cellulose containing quaternary ammonium salt. The tylosin residue contained high levels of antibiotic residues and some residual microorganisms, which could affect the subsequent fermentation process and potentially pollute the soil and plants. The material obtained after precipitation is a Fenton-type catalyst, which can catalyze the generation of free radicals from hydrogen peroxide to degrade tylosin remaining in the bacterial residue. Grafting with quaternary ammonium salt has a good antibacterial effect. During the process of catalyst degradation of tylosin, the cellulose on the surface of magnetic iron oxide will be degraded to a certain extent. The degradation of cellulose can also provide components for subsequent fertilizers. Magnetic iron oxide can be separated by a magnet, so the addition of carboxymethyl cellulose from magnetic iron oxide will not affect the subsequent process. The preparation process of this invention can efficiently remove tylosin remaining in bacterial residue.

[0068] It will be apparent to those skilled in the art that the present 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 its spirit or essential characteristics. 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. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A process for preparing organic fertilizer from tylosin inoculant residue, characterized in that, The preparation steps include the following: (1) Mix ferrous chloride tetrahydrate, ferrous chloride hexahydrate and pure water in a mass ratio of 1:2.6:

100. Under nitrogen protection, heat to 90℃ and stir for 5-10 min. Then add sodium carboxymethyl cellulose solution and 25wt% ammonia water at 10-11 times the mass of ferrous chloride tetrahydrate. After reacting for 30 min, cool to room temperature. After separation by magnet and washing with pure water 3-4 times, pre-modified carboxymethyl cellulose is obtained. (2) Mix pre-modified carboxymethyl cellulose, isopropanol, and pure water at a mass ratio of 1:(12-15):0.5, add 0.37 g / L sodium hydroxide solution at 12-15 times the mass of modified carboxymethyl cellulose, react for 30 min, raise the temperature to 50-60℃, add 3-chloro-2-hydroxypropyltrimethylammonium chloride at 0.1-0.3 times the mass of modified carboxymethyl cellulose, react for 2-3 h, cool to room temperature after the reaction is completed, and obtain modified carboxymethyl cellulose by vacuum drying after rotary evaporation under reduced pressure. (3) Mix the pre-modified carboxymethyl cellulose, hydrogen peroxide and tylosin bacterial residue at a mass ratio of 1:(20-30):(2-3), react under sealed conditions at 95-110℃ for 60-90 min, after the reaction is completed, separate by magnet, retain the filtrate after solid-liquid separation, and obtain the pretreated bacterial residue by vacuum drying; (4) After mixing the pretreated bacterial residue and auxiliary materials at a mass ratio of 1:(2-4), the mixture is aerobic composted and fermented, then dried, crushed and granulated to obtain organic fertilizer.

2. The process for preparing organic fertilizer from tylosin inoculant 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 at 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 × 10⁻⁶. 3 The degree of substitution is 1.

3. The process for preparing organic fertilizer from tylosin inoculant 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. The process for preparing organic fertilizer from tylosin inoculant residue according to claim 1, characterized in that, The auxiliary material mentioned 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%.

5. The process for preparing organic fertilizer from tylosin inoculant residue according to claim 1, characterized in that, The aerobic composting fermentation process described in step (4) is as follows: after the composting temperature is raised to 55-65℃, it is kept warm for 3-4 days, and then the pile is turned over. The turning frequency is once every 3-4 days. The fermentation takes 15-17 days, and the temperature is lowered to 30-40℃. The fermentation time is 3-5 days.

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