CN114535269B - Innocent treatment method for antibiotic fungus residues and application thereof - Google Patents
Innocent treatment method for antibiotic fungus residues and application thereof Download PDFInfo
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- KNIWPHSUTGNZST-UHFFFAOYSA-N polymyxin E2 Natural products CC(C)CCCCC(=O)NC(CCN)C(=O)NC(C(C)O)C(=O)NC(CCN)C(=O)NC1CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C(CC(C)C)NC(=O)C(CCN)NC1=O KNIWPHSUTGNZST-UHFFFAOYSA-N 0.000 description 3
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- ONUMZHGUFYIKPM-MXNFEBESSA-N telavancin Chemical compound O1[C@@H](C)[C@@H](O)[C@](NCCNCCCCCCCCCC)(C)C[C@@H]1O[C@H]1[C@H](OC=2C3=CC=4[C@H](C(N[C@H]5C(=O)N[C@H](C(N[C@@H](C6=CC(O)=C(CNCP(O)(O)=O)C(O)=C6C=6C(O)=CC=C5C=6)C(O)=O)=O)[C@H](O)C5=CC=C(C(=C5)Cl)O3)=O)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](NC(=O)[C@@H](CC(C)C)NC)[C@H](O)C3=CC=C(C(=C3)Cl)OC=2C=4)O[C@H](CO)[C@@H](O)[C@@H]1O ONUMZHGUFYIKPM-MXNFEBESSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses an antibiotic fungus dreg harmless treatment method and application thereof. According to the invention, physical and chemical pretreatment processes such as crushing and sieving, peroxide mixing, flash evaporation and spray drying, steam and air ventilation are adopted, and the synergistic effect among the processes is utilized, so that the efficient degradation of antibiotics in the fungus residues is realized, finally, fermentation materials are added into the pretreated fungus residues and uniformly mixed, and then, a compound mixed strain is inoculated for composting solid fermentation, so that the harmless treatment of the antibiotic fungus residues is realized, the content of the antibiotics in the harmless antibiotic fungus residues obtained by the treatment method is reduced to below 1mg/kg, and the degradation rate of the antibiotics reaches 99.99%; meanwhile, the invention solves the problem of high bacterial dreg treatment cost in the production process of the related enterprises, can save a large amount of treatment cost and bring certain economic benefit; in addition, the peroxide used in the invention can be finally converted into nutrient elements in the organic fertilizer, thereby realizing the full utilization of raw materials.
Description
Technical Field
The invention belongs to the technical field of solid waste disposal and resource recycling, and particularly relates to an antibiotic fungus dreg harmless treatment method and application thereof.
Background
The solid waste produced in the antibiotic production process is fungus dreg, and the main components of the solid waste are mycelium of antibiotic producing fungus, unused culture medium, metabolic products produced in the fermentation process, degradation products of the culture medium, a small amount of antibiotics and the like. The residual culture medium, a small amount of antibiotics and degradation products thereof in the waste bacterial residues of the antibiotic fermentation have potential harm to the ecological environment, and the waste bacterial residues are regarded as one of main public hazards in the production of antibiotics by the international society, and meanwhile, the organic matter content of the bacterial residues is higher, so that secondary fermentation, color blackening, bad smell generation and serious environmental influence can be caused, so that people have actively searched for a pollution control method with economy, high efficiency and large treatment capacity for a long time.
The method is a large country for producing antibiotic bulk drugs, has large production amount of antibiotic fungus residues and high treatment difficulty, and is a difficult problem to be solved by the current pharmaceutical enterprises because the antibiotic fungus residues belong to dangerous solid wastes and are reasonably and safely disposed. In the research of the treatment method of the antibiotic residues, more research and exploration are carried out in China, and a lot of progress is achieved, but the method has the defects in the thorough removal of the antibiotic residues, the treatment cost and the applicability of the method. In the treatment method of antibiotic residues, more biodegradation researches are carried out, for example, microorganisms which can degrade antibiotics efficiently are directly separated and screened, and the screened microorganisms are utilized for degradation; there are also treatments using natural microbial flora, such as the flora of microorganisms during composting or the flora of microorganisms during anaerobic biogas fermentation, but none of them is able to clean residual antibiotics stably and thoroughly. The content of residual antibiotics in the antibiotic residues is generally 0.3-0.5%, the unit of activity per kilogram is millions or even tens of millions, and the complete degradation is difficult to realize due to slow biodegradation starting and difficult complete degradation only by biodegradation facing the high content of antibiotics. In addition, microbial resistance is highly correlated with the ability to decompose the drug, which means that the resistance is strong, and when a single microorganism, especially a single prokaryotic microorganism, has a strong degrading effect, it is also predictive of its high resistance and risk of environmental release.
In addition, physical methods such as high-temperature high-pressure treatment and high-energy electron beams can directly destroy the structure of antibiotics, and the method is used for removing residual antibiotics of antibiotic residues, is an effective method, but has the disadvantages of high investment cost and high operation cost, and is not beneficial to large-scale application. The chemical methods such as strong acid, strong alkali, strong oxidant and the like can achieve a certain effect when applied to the treatment of the antibiotic fungus residues, but the problems that the treatment is not thorough, the subsequent treatment difficulty of the fungus residues is increased or the resource utilization cannot be realized after the acid-base action and the like exist.
In view of the above, it is necessary to provide a harmless treatment method for antibiotic residues to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an antibiotic fungus dreg harmless treatment method and application thereof. Solves the problems that the existing physical methods such as high-temperature high-pressure treatment, high-energy electron beams and the like, the chemical methods such as strong acid, strong alkali, strong oxidant and the like, and the single microbial degradation method can not thoroughly remove antibiotics in antibiotic residues or can not be recycled.
The invention aims to provide a harmless treatment method for antibiotic residues.
An antibiotic fungus dreg harmless treatment method comprises the following steps:
S1, physicochemical pretreatment: crushing and sieving antibiotic residues, adding peroxide and mixing to obtain a mixture, then carrying out flash evaporation and spray drying on the mixture to obtain powder, and finally introducing steam and air into the powder for reaction to obtain pretreated residues;
s2, biological post-treatment: and (2) adding fermentation materials into the pretreated bacterial residues obtained in the step (S1) and uniformly mixing, and then inoculating compound mixed strains for composting solid-state fermentation, thereby realizing innocuous treatment of the antibiotic bacterial residues.
Further, in step S1, the water content of the antibiotic residues is 50-85%.
Further, in the step S1, the pore diameter of the sieving screen is 1-10 meshes.
Further, in the step S1, the peroxide is selected from one of calcium peroxide, sodium peroxide and magnesium peroxide, and the addition amount of the peroxide is 5-20% of the dry weight of the antibiotic fungi residues.
Further, in the step S1, the flash evaporation and spray drying temperature is 160-200 ℃, the air quantity is 30-50 Hz, and the feeding speed is 0.2-1 ton/h.
Further, in the step S1, the steam flow is 1-100 kg/h, the air flow is 0.2-1.0 m 3/h, and the reaction time is 1-2 days.
Further, in step S2, the fermentation material ratio (the ratio of the weight of each material to the weight of the antibiotic residues) is as follows: 10 to 30 percent of phosphoric acid, 30 to 60 percent of water, 15 to 40 percent of chaff powder, 5 to 10 percent of corn starch, 1 to 5 percent of corn powder, 5 to 10 percent of rice bran and 6.0 to 9.0 of pH.
Further, in step S2, the ratio of each single strain in the compound mixed strain is as follows in parts by weight: 2-4 parts of flavobacterium odoratum, 9-11 parts of aspergillus niger, 9-11 parts of aspergillus oryzae, 9-11 parts of trichoderma, 4-6 parts of saccharomyces cerevisiae and 7-9 parts of bacillus amyloliquefaciens; the inoculation amount of the compound mixed strain is 0.2-2%.
Further, in step S2, the composting solid-state fermentation conditions are as follows: after stacking for 24-48 h, turning and aerating after the temperature reaches above 40 ℃, wherein the number of times of turning is 1-2 times per day, and the fermentation time is 15-30 days.
According to the invention, firstly, the antibiotic residues are crushed and sieved to obtain fine particles with increased specific surface area, so that the peroxide can fully contact the antibiotics in the antibiotic residues, as the antibiotic residues contain a large amount of water, after the two are mixed, a part of peroxide generates hydroxide with alkalinity, the structure of antibiotic molecules can be obviously destroyed by utilizing the strong oxidizing property of the peroxide and the strong alkalinity of the hydroxide, thereby reducing the residue of the antibiotics in the residues, and further, the mixture of the peroxide and the antibiotic residues is flash-dried, on one hand, the mixture is dispersed under the effects of impact, friction and shearing force in a flash evaporation dryer, so that the peroxide and the antibiotics can be fully contacted, and high-efficiency degradation is realized; on the other hand, the flash evaporation high temperature can further activate peroxide to generate free radicals with stronger activity, so as to strengthen the degradation effect on antibiotics; and then, introducing steam and air into the powder subjected to flash evaporation drying to react, wherein unreacted peroxide is subjected to synergistic effect under the conditions of the steam and the air, so that antibiotics in the fungus residues are further degraded, and the pretreatment process is completed; and finally, adding fermentation materials into the pretreated bacterial residues, uniformly mixing, and inoculating compound mixed strains for composting and solid-state fermentation, thereby realizing harmless treatment of the antibiotic bacterial residues.
The invention also provides application of the harmless antibiotic residues obtained by the harmless treatment method of the antibiotic residues in preparation of organic fertilizers.
Compared with the prior art, the invention has the following advantages:
1) According to the invention, physical and chemical pretreatment processes such as crushing and sieving, peroxide mixing, flash evaporation and spray drying, steam and air ventilation are adopted, and the synergistic effect among the processes is utilized, so that the efficient degradation of antibiotics in the fungus residues is realized, finally, fermentation materials are added into the pretreated fungus residues and uniformly mixed, and then, a compound mixed strain is inoculated for composting solid fermentation, so that the harmless treatment of the antibiotic fungus residues is realized, the content of the antibiotics in the harmless antibiotic fungus residues obtained by the treatment method is reduced to below 1mg/kg, and the degradation rate of the antibiotics reaches 99.99%;
2) The raw materials used in the invention are all easily available and environment-friendly materials, and crop straws and the like which are not easy to treat in agriculture can be used as compost fermentation auxiliary materials, so that the invention has more application value; meanwhile, the problem of high bacterial dreg treatment cost in the production process of related enterprises is solved, a large amount of treatment cost can be saved, and certain economic benefit is brought; in addition, the peroxide used in the invention can be finally converted into nutrient elements in the organic fertilizer, thereby realizing the full utilization of raw materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
Conventional reagents and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
An antibiotic fungus dreg harmless treatment method comprises the following steps:
S1, physicochemical pretreatment: weighing 2000kg of tylosin residues, wherein the water content of the tylosin residues is 80%, crushing the tylosin residues through a 1-10-mesh screen, adding 380kg of calcium peroxide, mixing to obtain a mixture, then carrying out flash evaporation and spray drying on the mixture, wherein the flash evaporation and spray drying temperature is 200 ℃, the air quantity is 50Hz, the feeding speed is 1 ton/h, obtaining powder, and finally introducing steam and air into the powder for reaction, wherein the steam flow is 100kg/h, the air flow is 1.0m 3/h, and the reaction time is 2 days, so as to obtain pretreated residues;
After the teviologen residues are subjected to physicochemical pretreatment, the teviologen content is degraded from 8000mg/kg to 89.5mg/kg, and the degradation rate is 98.9%.
S2, biological post-treatment: adding fermentation materials into the pretreated bacterial residues obtained in the step S1, and uniformly mixing, wherein the ratio of the fermentation materials (the ratio of the weight of each material to the weight of the antibiotic bacterial residues) is as follows: 10 to 30 percent of phosphoric acid, 30 to 60 percent of water, 15 to 40 percent of chaff powder, 5to 10 percent of corn starch, 1 to 5 percent of corn powder, 5to 10 percent of rice bran and 6.0 to 9.0 of pH; then inoculating the compound mixed strain (2-4 parts of flavobacterium odoratum, 9-11 parts of aspergillus niger, 9-11 parts of aspergillus oryzae, 9-11 parts of trichoderma, 4-6 parts of saccharomyces cerevisiae and 7-9 parts of bacillus amyloliquefaciens) according to the inoculation amount of 2% to perform composting solid state fermentation, wherein the composting solid state fermentation conditions are as follows: after 48h of stacking, turning and aerating after the temperature reaches above 40 ℃, wherein the temperature reaches 50 ℃ on the 3 rd day, the high-temperature duration (not less than 50 ℃) is maintained for 10 days, the temperature is above 60 ℃ for 3 consecutive days, the highest temperature is 63.5 ℃, the number of times of turning is 2 times per day, and the fermentation time is 30 days; thereby realizing innocent treatment of the antibiotic residues.
After biological post-treatment, the content of the teicoplanin in the pretreated teicoplanin residues is reduced to below 1 mg/kg.
Example 2
An antibiotic fungus dreg harmless treatment method comprises the following steps:
S1, physicochemical pretreatment: weighing 200kg of tylosin residues, wherein the water content of the tylosin residues is 65%, crushing the tylosin residues through a 1-10-mesh screen, adding 20kg of sodium peroxide, mixing to obtain a mixture, then carrying out flash evaporation and spray drying on the mixture, wherein the flash evaporation and spray drying temperature is 180 ℃, the air quantity is 40Hz, the feeding speed is 0.6 ton/h, obtaining powder, and finally, introducing steam and air into the powder for reaction, wherein the steam flow is 50kg/h, the air flow is 0.6m 3/h, and the reaction time is 1.5 days, so as to obtain pretreated bacterial residues;
after the tylosin dreg is subjected to physicochemical pretreatment, the tylosin content is degraded from 2531mg/kg to 94mg/kg, and the degradation rate is 96.3%.
S2, biological post-treatment: adding fermentation materials into the pretreated bacterial residues obtained in the step S1, and uniformly mixing, wherein the ratio of the fermentation materials (the ratio of the weight of each material to the weight of the antibiotic bacterial residues) is as follows: 10 to 30 percent of phosphoric acid, 30 to 60 percent of water, 15 to 40 percent of chaff powder, 5to 10 percent of corn starch, 1 to 5 percent of corn powder, 5to 10 percent of rice bran and 6.0 to 9.0 of pH; then inoculating the compound mixed strain (2-4 parts of flavobacterium odoratum, 9-11 parts of aspergillus niger, 9-11 parts of aspergillus oryzae, 9-11 parts of trichoderma, 4-6 parts of saccharomyces cerevisiae and 7-9 parts of bacillus amyloliquefaciens) according to the inoculation amount of 1% to perform composting solid state fermentation, wherein the composting solid state fermentation conditions are as follows: after 48h of stacking, turning and aerating after the temperature reaches above 40 ℃, wherein the temperature reaches 50 ℃ on the 3 rd day, the high-temperature duration (not less than 50 ℃) is maintained for 10 days, the temperature is above 60 ℃ for 3 consecutive days, the highest temperature is 61.3 ℃, the number of times of turning is 1 time per day, and the fermentation time is 21 days; thereby realizing innocent treatment of the antibiotic residues.
After the pretreated tylosin residues are subjected to biological post-treatment, the tylosin content is reduced to below 1 mg/kg.
Example 3
An antibiotic fungus dreg harmless treatment method comprises the following steps:
S1, physicochemical pretreatment: 400kg of colistin bacteria residue is weighed, the water content of the colistin bacteria residue is 55%, the colistin bacteria residue is crushed by a 1-10-mesh screen, then 20kg of magnesium peroxide is added and mixed to obtain a mixture, the mixture is subjected to flash evaporation and spray drying, the flash evaporation and spray drying temperature is 160 ℃, the air quantity is 30Hz, the feeding speed is 0.2 ton/h, powder is obtained, finally, steam and air are introduced into the powder for reaction, the steam introduction flow is 15kg/h, the air introduction air quantity is 0.2m 3/h, and the reaction time is 1 day, so as to obtain pretreated bacteria residue;
after the teviologen residues are subjected to physicochemical pretreatment, the teviologen content is degraded from 5321mg/kg to 244.7mg/kg, and the degradation rate is 95.4%.
S2, biological post-treatment: adding fermentation materials into the pretreated bacterial residues obtained in the step S1, and uniformly mixing, wherein the ratio of the fermentation materials (the ratio of the weight of each material to the weight of the antibiotic bacterial residues) is as follows: 10 to 30 percent of phosphoric acid, 30 to 60 percent of water, 15 to 40 percent of chaff powder, 5 to 10 percent of corn starch, 1 to 5 percent of corn powder, 5 to 10 percent of rice bran and 6.0 to 9.0 of pH; then inoculating the compounded mixed strain (2-4 parts of flavobacterium odoratum, 9-11 parts of aspergillus niger, 9-11 parts of aspergillus oryzae, 9-11 parts of trichoderma, 4-6 parts of saccharomyces cerevisiae and 7-9 parts of bacillus amyloliquefaciens) according to the inoculation amount of 0.5% for composting solid state fermentation, wherein the composting solid state fermentation conditions are as follows: after 48h of stacking, turning and aerating after the temperature reaches above 40 ℃, wherein the temperature reaches 50 ℃ on the 3 rd day, the high-temperature duration (not less than 50 ℃) is maintained for 10 days, the temperature is above 60 ℃ for 3 continuous days, the highest temperature is 60.2 ℃, the number of times of turning is 1 time per day, and the fermentation time is 18 days; thereby realizing innocent treatment of the antibiotic residues.
After biological post-treatment, the content of the teicoplanin in the pretreated teicoplanin residues is reduced to below 1 mg/kg.
Comparative example 1
The physicochemical pretreatment method in the innocuous treatment method of the antibiotic residues is basically the same as that of the embodiment 1, except that no peroxide is added.
As a result, the tylosin residue is subjected to physicochemical pretreatment, the tylosin content is degraded from 8000mg/kg to 5584mg/kg, and the degradation rate is 30.5%.
Comparative example 2
The physicochemical pretreatment method in the innocuous treatment method of the antibiotic residues is basically the same as that of the embodiment 1, except that the flash evaporation drying process is absent.
As a result, the tylosin residue is subjected to physicochemical pretreatment, the tylosin content is degraded from 8000mg/kg to 1560mg/kg, and the degradation rate is 80.5%.
Comparative example 3
The physicochemical pretreatment method in the innocuous treatment method of antibiotic residues is basically the same as that of the embodiment 1, except that the process of introducing steam and air for reaction is absent.
As a result, it was found that the tylosin residue was degraded from 8000mg/kg to 1968mg/kg after the physicochemical pretreatment, and the degradation rate was 75.4%.
As can be seen from the experimental results in the comparative examples 1 to 3, the degradation rate of the telavancin bacterial residues is greatly reduced without adding peroxide, flash drying or any step of reaction by introducing steam and air, and further shows that the processes are synergistic, so that the efficient degradation of antibiotics in the bacterial residues is realized.
Example 4 Performance index test of materials after biological post-treatment of Mushroom residues
The harmless antibiotic residues prepared in examples 1 to 3 were tested according to the NY525-2021 standard, and the performance index test results are shown in the following Table 1:
TABLE 1 results of Performance index test of materials after biological post-treatment of bacterial residues
From the data in the table, the harmless antibiotic residues obtained by the method of the invention completely meet the detection standard of the organic fertilizer, so that the harmless antibiotic residues have good application prospect in preparing the organic fertilizer.
The above examples are only specific embodiments of the present invention for illustrating the technical solution of the present invention, but not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the foregoing examples, it will be understood by those skilled in the art that the present invention is not limited thereto: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (7)
1. The innocent treatment method of the antibiotic fungus residues is characterized by comprising the following steps:
S1, physicochemical pretreatment: crushing and sieving antibiotic residues, adding peroxide and mixing to obtain a mixture, then carrying out flash evaporation and spray drying on the mixture to obtain powder, and finally introducing steam and air into the powder for reaction to obtain pretreated residues;
the water content of the antibiotic residues is 50-85%;
the flash evaporation and spray drying temperature is 160-200 ℃, the air quantity is 30-50 Hz, and the feeding speed is 0.2-1 ton/h;
The steam flow is 1-100 kg/h, the air flow is 0.2-1.0 m 3/h, and the reaction time is 1-2 days;
s2, biological post-treatment: and (2) adding fermentation materials into the pretreated bacterial residues obtained in the step (S1) and uniformly mixing, and then inoculating compound mixed strains for composting solid-state fermentation, thereby realizing innocuous treatment of the antibiotic bacterial residues.
2. The method for innocent treatment of antibiotic residues according to claim 1, wherein in the step S1, the aperture of the sieving screen is 1-10 meshes.
3. The method for innocuous treatment of antibiotic residues according to claim 1, wherein in the step S1, the peroxide is selected from one of calcium peroxide, sodium peroxide and magnesium peroxide, and the addition amount of the peroxide is 5-20% of the dry weight of the antibiotic residues.
4. The innocent treatment method for antibiotic residues according to claim 1, wherein in the step S2, the fermentation material ratio (the ratio of the weight of each material to the weight of the antibiotic residues) is as follows: 10 to 30 percent of phosphoric acid, 30 to 60 percent of water, 15 to 40 percent of chaff powder, 5 to 10 percent of corn starch, 1 to 5 percent of corn powder, 5 to 10 percent of rice bran and 6.0 to 9.0 of pH.
5. The innocent treatment method of the antibiotic residues according to claim 1, wherein in the step S2, the ratio of the single bacteria in the compound mixed bacteria is as follows in parts by weight: 2-4 parts of flavobacterium odoratum, 9-11 parts of aspergillus niger, 9-11 parts of aspergillus oryzae, 9-11 parts of trichoderma, 4-6 parts of saccharomyces cerevisiae and 7-9 parts of bacillus amyloliquefaciens; the inoculation amount of the compound mixed strain is 0.2-2%.
6. The method for innocuous treatment of antibiotic residues according to claim 1, wherein in step S2, the solid state fermentation conditions of the compost are as follows: after stacking for 24-48 h, turning and aerating after the temperature reaches above 40 ℃, wherein the number of times of turning is 1-2 times per day, and the fermentation time is 15-30 days.
7. The use of the innocuous antibiotic residues obtained by the innocuous treatment method of the antibiotic residues according to any one of claims 1 to 6 in preparing organic fertilizer.
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