CN113087552A - Method for preparing organic fertilizer from antibiotic bacterium residues and product thereof - Google Patents

Method for preparing organic fertilizer from antibiotic bacterium residues and product thereof Download PDF

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CN113087552A
CN113087552A CN202110398142.8A CN202110398142A CN113087552A CN 113087552 A CN113087552 A CN 113087552A CN 202110398142 A CN202110398142 A CN 202110398142A CN 113087552 A CN113087552 A CN 113087552A
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antibiotic
residues
organic fertilizer
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organic
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CN113087552B (en
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戴晓虎
刘惠玲
蔡辰
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Tongji University
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • A62D3/178Microwave radiations, i.e. radiation having a wavelength of about 0.3 cm to 30cm
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F3/00Fertilisers from human or animal excrements, e.g. manure
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/40Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

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  • Fertilizers (AREA)

Abstract

The invention relates to the technical field of harmless treatment of antibiotic mushroom dregs, in particular to a method for preparing an organic fertilizer from antibiotic mushroom dregs and a product thereof; the organic fertilizer is obtained by mixing antibiotic fungi residues after microwave treatment under ultrasonic conditions with organic solid wastes, drying after aerobic composting fermentation, crushing and granulating. According to the invention, through microwave combined ultrasonic treatment, residual antibiotics in the antibiotic residues are removed, meanwhile, the reduction of resistance genes in the antibiotic residues is realized, and the problem of secondary pollution caused by the reuse of the antibiotic residues is avoided. Experiments prove that the antibiotic residue in the harmless antibiotic residues obtained by the method is less than 1mg/kg, the antibiotic removal efficiency can be 99.99% within 40min, and the resistance gene removal rate is more than 6 log.

Description

Method for preparing organic fertilizer from antibiotic bacterium residues and product thereof
Technical Field
The invention relates to the technical field of harmless treatment of antibiotic mushroom dregs, in particular to a method for preparing an organic fertilizer from antibiotic mushroom dregs and a product thereof.
Background
The antibiotic fungi residues refer to mycelium waste residues generated in the antibiotic fermentation production process, belong to industrial wastes, and mainly comprise mycelium, metabolites generated in the fermentation process, degradation products of a culture medium, residual organic solvents, residual antibiotics and the like. Antibiotics are commonly used to promote growth and prevent disease in livestock, but abuse of antibiotics and subsequent treatment with incorrect drugs can lead to the introduction of antibiotics and their metabolites and conversion products into hospital and municipal sewage. In the environment, antibiotics are not only chemical pollutants, but also can induce the generation of resistance genes and drug-resistant bacteria, and even generate 'super bacteria' carrying multiple resistance genes, so that the antibiotic treatment is ineffective, and potential harm is caused to the ecological environment and human health; therefore, the antibiotic residues contained in the antibiotic residues cause the risk of bacterial drug resistance in the environment when the antibiotic residues are directly recycled, and therefore the antibiotic residues and the resistance genes must be removed through treatment before harmless utilization of the antibiotic residues can be achieved. If the treatment is improper, the ecological environment and the human health can be seriously harmed. In 2008, newly revised national hazardous waste records are listed in antibiotic fungi residues, and the antibiotic fungi residues belong to culture medium waste in the production process of chemical bulk drugs and need to be managed according to the hazardous waste. Therefore, how to reasonably treat the antibiotic residues, the method for harmlessly treating the antibiotic residues is provided, and the solution of the antibiotic residues is an urgent task.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing an organic fertilizer from antibiotic residues, which is characterized in that residual antibiotics in the antibiotic residues are removed and simultaneously resistance genes in the antibiotic residues are reduced by microwave combined ultrasonic treatment, so that the problem of secondary pollution caused by recycling of the antibiotic residues is avoided.
The method for preparing organic fertilizer from antibiotic fungi residues comprises the steps of mixing the antibiotic fungi residues with organic solid wastes after microwave treatment under ultrasonic conditions, drying after aerobic composting fermentation, crushing and granulating to obtain the organic fertilizer.
Further, the water content of the antibiotic bacterial residues is 80-90%, the ultrasonic frequency is 100-.
Further, the mixing mass ratio of the antibiotic bacterium residues and the organic solid wastes obtained after the microwave treatment under the ultrasonic condition is (3-5) to (1-2), the water content is adjusted to 60-65% after mixing, the aerobic composting fermentation is carried out for 25-35 days after the pH value is 7.0-7.5, and the piles are turned over once every 3-7 days.
Furthermore, the antibiotic residues are one of aminoglycoside antibiotic residues, tetracyclic antibiotic residues, tylosin residues and erythrocin residues, and the organic solid waste is one or a mixture of poultry and livestock excrement, municipal sludge, kitchen waste and agricultural and forestry waste.
Further, before the microwave treatment under ultrasonic conditions, the following pretreatment was performed: adding oxidant into the antibiotic residues, and carrying out oxidation treatment for 0.5-1h at the temperature of 50-90 ℃.
Further, the antioxidant is persulfate, and the molar ratio of the oxidant to the antibiotics in the antibiotic fungi residues is (15-30): 1.
according to the second technical scheme, the organic fertilizer is prepared by the method for preparing the organic fertilizer from the antibiotic bacterium residues.
The technical principle of the invention is as follows:
moisture in the mushroom dregs can efficiently absorb microwave radiation and is quickly converted into heat energy, so that the temperature of the mushroom dregs is increased in a short time, and the high temperature is favorable for decomposing antibiotics in the mushroom dregs, so that the aim of removing the antibiotic residues in the mushroom dregs is fulfilled; the microwave radiation can also promote the wall breaking of mycelium in the mushroom dregs, effectively destroy the cell structure, release cell walls and main components in cells, and cause the relaxation, the breaking and the recombination of hydrogen bonds in RNA and DNA in the released microorganism, thereby destroying the original double-stranded DNA structure and eliminating resistance genes; and the microwave treatment under the cavitation condition of the ultrasound is helpful to promote the hydrogen bond fracture, weaken the direct recombination and combination of the DNA structure and strengthen the elimination effect of the microwave on the resistance gene. Meanwhile, the ultrasonic wave can generate high-energy cavitation bubbles under the action of ultrasonic cavitation, so that water molecules can be split into hydroxyl free radicals, and the oxidative decomposition of antibiotics is further promoted by the pyrolysis of the high-energy cavitation bubbles and the oxidation of the hydroxyl free radicals.
In the preferred scheme of the invention, the preoxidation treatment under the heating condition is carried out on the antibiotic residues before the microwave treatment under the ultrasonic condition is carried out, the strong oxidizing property of the oxidizing agent can destroy the molecular structure of the antibiotic, effectively reduce the antibiotic residue in the antibiotic residues and improve the treatment efficiency of the subsequent ultrasonic-microwave combined treatment of the antibiotic residues.
The harmless antibiotic residues obtained by the harmless treatment method of the antibiotic residues reserve organic nutrient substances which are beneficial to the growth of plants, such as original protein, amino acid and the like in the antibiotic residues, and are ideal organic fertilizer raw materials, but the obtained harmless antibiotic residues are not easy to be directly absorbed and utilized by the plants when being directly used as the organic fertilizer due to the overlarge molecular weight of the nutrient substance components; therefore, the obtained harmless fungus residue and organic solid waste are mixed uniformly and then are subjected to aerobic composting fermentation, so that macromolecular substances in the harmless fungus residue are promoted to be degraded, and the fertilizer efficiency and the bioavailability of the organic fertilizer are improved.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, organic nutrient substances such as polysaccharide, protein and amino acid beneficial to plant growth can be reserved on the premise of ensuring efficient removal of antibiotic residues in the antibiotic residues, and selective removal of organic matters in the residues is realized; meanwhile, the resistance genes in the antibiotic fungi residues are effectively removed in the ultrasonic and microwave combined treatment process, compared with other waste treatment technologies, the method is simple and efficient, excessive chemical reagents and harsh conditions are not needed, secondary pollution is avoided, and the method is a clean and sustainable technology. Experiments prove that the antibiotic residue in the harmless antibiotic residues obtained by the method is less than 1mg/kg, the antibiotic removal efficiency can be 99.99% within 40min, and the resistance gene removal rate is more than 6 log.
According to the invention, the antibiotic bacteria residues and the organic solid waste are subjected to mixed aerobic composting fermentation process, so that the bioavailability of the harmless bacteria residues and bacteria residues is improved, the secondary utilization of the organic solid waste is realized, and the technical problem of difficulty in organic solid waste treatment in the prior art is solved.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Adjusting the water content of antibiotic bacterium residues with the residual quantity of the gentamicin of 2600mg/kg to 85%, then placing the antibiotic bacterium residues in a microwave ultrasonic reaction, wherein the water content is adjusted to 65% after the antibiotic bacterium residues are uniformly mixed with organic solid wastes according to the mass ratio of 3:1 under the conditions of acoustic frequency of 150KHz, microwave power of 700W and ultrasonic condition, carrying out aerobic composting fermentation for 30 days after the pH value is 7.5, turning the compost once every 5 days, and drying, crushing and granulating the compost fermentation products to obtain the organic fertilizer.
Example 2
Adjusting the water content of the antibiotic residues to 80%, placing the antibiotic residues in a microwave ultrasonic reaction, wherein the microwave treatment is carried out for 10min under the conditions of acoustic frequency 200KHz, microwave power 1000W and ultrasonic wave, then the antibiotic residues are uniformly mixed with organic solid wastes according to the mass ratio of 3:1, the water content is adjusted to 65%, after the pH value is 7.0, aerobic composting fermentation is carried out for 35 days, during which, the compost is turned over once every 5 days, and the compost fermentation products are dried, crushed and granulated to obtain the organic fertilizer.
Example 3
The difference from example 1 is that the ultrasonic conditions were omitted during the microwave treatment.
Example 4
The difference from example 1 is that the microwave step is omitted and only sonication is used.
Example 5
The difference from example 1 is that the antibiotic residues were pretreated as follows before being subjected to microwave treatment under ultrasonic conditions: adding sodium persulfate into the antibiotic residues (the molar ratio of the sodium persulfate to the antibiotics in the antibiotic residues is 20: 1), and carrying out oxidation treatment for 0.5h at the temperature of 80 ℃.
Example 6
The difference from example 1 is that the antibiotic residues were pretreated as follows before being subjected to microwave treatment under ultrasonic conditions: adding sodium persulfate and copper powder (the molar ratio of the sodium persulfate to the antibiotics in the antibiotic fungi residues to the copper powder is 20: 1: 5), and carrying out oxidation treatment for 0.5h at the temperature of 80 ℃.
The preparation method of the copper powder comprises the following steps: adding nano iron with the same molar weight as copper ions into a copper sulfate solution with the concentration of 10g/L at 40 ℃ under the condition of stirring, continuously stirring until the solution is reddish brown, filtering to obtain an upper layer substance, and drying to obtain the copper powder particles.
Example 7
The difference from example 1 is that the antibiotic residues were pretreated as follows before being subjected to microwave treatment under ultrasonic conditions: adding sodium persulfate and copper powder (the molar ratio of the sodium persulfate to the antibiotics in the antibiotic fungi residues to the copper powder is 20: 1: 5), and carrying out oxidation treatment for 0.5h at the temperature of 80 ℃.
The preparation method of the copper powder comprises the following steps: adding nano iron with twice molar weight of copper ions into copper sulfate solution with concentration of 10g/L at 40 ℃ under the condition of stirring, continuously stirring until the solution is reddish brown, filtering to obtain an upper layer substance, and drying to obtain the copper powder particles.
Example 8
The same as example 1, except that 8% (w/w) of a mixture containing 10% of harmless antibiotic residues and organic solid waste was inoculated before composting fermentation was carried out8cfu/mL Lignin degrading bacteria and 106cfu/mL mixed strain liquid of azotobacter.
Example 9
The difference from the example 1 is that the antibiotic fungi residues are directly dried, crushed and granulated after being treated by microwave under the ultrasonic condition to obtain the organic fertilizer.
Performing antibiotic and resistance gene removal rate detection on the organic fertilizer obtained in the examples 1-9, wherein the resistance gene removal rate is that DNA on a filter membrane is extracted by using a Kit (TIANAmp Silo DNA Kit) according to the instruction, and then the abundance of the resistance gene is detected by using a quantitative PCR method, and the specific method is a common technical means in the field and is not described herein; the results are shown in Table 1;
the results of antibiotic and resistance gene testing of the antibiotic residues treated in examples 1-7 before composting are shown in Table 1.
TABLE 1
Figure BDA0003019345820000051
Figure BDA0003019345820000061
The data in the table 1 show that the ultrasonic and microwave combined treatment can obviously improve the harmless treatment efficiency of the antibiotic residues, so that the antibiotic residues and the resistance genes in the antibiotic residues are obviously reduced, and the compost fermentation is helpful for further reducing the residual quantity of the resistance genes in the antibiotic residues. And the antibiotic residues are subjected to preoxidation treatment before ultrasonic and microwave combined treatment, so that the harmless treatment efficiency of the antibiotic residues is further increased. In addition, in the process of preparing copper powder, because the added iron is excessive, the replaced copper particles are attached to the excessive iron surface to form a copper-iron mixture with a large amount of copper particles attached to the iron surface, on one hand, the loss of the copper particles during repeated use can be reduced, more importantly, the iron can also activate persulfate, and the two can generate interaction to enable the copper particles to play a role of catalytic active centers, so that the activation performance of the copper is improved, oxygen in water and air is activated, active oxygen with strong oxidation performance and cytotoxicity is generated, a series of active oxygen can damage cellular macromolecules, enzyme inhibition, lipid peroxidation, protein change and the like are further caused, and finally, the DNA or RNA structure in cells is damaged, the capability of dominating and transmitting resistance genes is lost, and the effect of removing the resistance genes is enhanced.
Selecting a certain citrus planting base, performing a fertilizer application comparison experiment on the organic fertilizer obtained in the examples 1-9, randomly selecting 100 citrus trees with the age of 4 years in a fruit forest, performing the experiment, dividing the citrus trees into 10 groups, taking the 1 st group as a blank experiment, performing hole application on the organic fertilizer prepared in the examples 1-9 in the groups 2-5 respectively, wherein the fertilizing amount is 1.5 kg/plant, and applying the organic fertilizer in 3 times. At maturity, the yield was recorded and the average was reported in table 2.
TABLE 2
Yield, kg/strain Yield, kg/strain
Example 1 86 Example 6 86
Example 2 85 Example 7 86
Example 3 86 Example 8 93
Example 4 82 Example 9 81
Example 5 83 Blank space 75
The data in the table 2 show that the mixing fermentation of the organic solid waste and the harmless antibiotic residues is beneficial to improving the fertilizer efficiency of the organic fertilizer, and the reason is that organic nutrients such as original protein and amino acid in the antibiotic residues, which are beneficial to the growth of plants, are reserved in the harmless antibiotic residues obtained by the harmless treatment method of the antibiotic residues, so that the harmless antibiotic residues are ideal organic fertilizer raw materials, but the harmless antibiotic residues are not easily absorbed and utilized by the plants when being directly used as the organic fertilizer due to the fact that the molecular weight of the nutrients in the harmless antibiotic residues is too large. And the compost fermentation is favorable for further degrading macromolecular substances into nutrient substances which are favorable for plants to absorb and utilize, and the quality of the organic fertilizer is improved. The addition of the strain liquid containing the nitrogen-fixing bacteria in the compost fermentation process is beneficial to further improvement of the fertilizer efficiency, and the reason is that in the compost, the nitrogen-fixing bacteria can convert nitrogen which cannot be directly utilized by plants into a form which can be absorbed and utilized so as to improve the agricultural quality of compost products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A method for preparing an organic fertilizer from antibiotic fungi residues is characterized in that the antibiotic fungi residues are subjected to microwave treatment under an ultrasonic condition, mixed with organic solid wastes, subjected to aerobic composting fermentation, dried, crushed and granulated to obtain the organic fertilizer.
2. The method for preparing the organic fertilizer from the antibiotic residues as claimed in claim 1, wherein the water content of the antibiotic residues is 80-90%, the ultrasonic frequency is 100 KHz and 1000W, and the microwave treatment time is 5-20min under the ultrasonic condition.
3. The method for preparing the organic fertilizer from the antibiotic fungi residues as claimed in claim 1, wherein the mixing mass ratio of the antibiotic fungi residues obtained after the microwave treatment under the ultrasonic condition to the organic solid waste is (3-5) to (1-2), the moisture content is adjusted to 60-65% after mixing, aerobic composting fermentation is carried out for 25-35 days after the pH value is 7.0-7.5, and the pile is turned over once every 3-7 days.
4. The method for preparing the organic fertilizer from the antibiotic residues according to claim 1, wherein the antibiotic residues are one of aminoglycoside antibiotic residues, tetracyclic antibiotic residues, tylosin residues and erythromycin residues, and the organic solid waste is one or a mixture of poultry and livestock excrement, municipal sludge, kitchen waste and agricultural and forestry waste.
5. The method for preparing the organic fertilizer from the antibiotic fungi residues as claimed in claim 1, which is characterized in that the following pretreatment is carried out before the microwave treatment under the ultrasonic condition: adding oxidant into the antibiotic residues, and carrying out oxidation treatment for 0.5-1h at the temperature of 50-90 ℃.
6. The method for preparing the organic fertilizer from the antibiotic fungi residues as claimed in claim 5, wherein the antioxidant is persulfate, and the molar ratio of the oxidant to the antibiotics in the antibiotic fungi residues is (15-30): 1.
7. an organic fertilizer prepared by the method for preparing the organic fertilizer by using the antibiotic fungi residues according to any one of claims 1 to 6.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337496A (en) * 2017-08-09 2017-11-10 哈尔滨工业大学 A kind of method that organic fertilizer is produced using tylosin dreg
CN110981563A (en) * 2019-12-11 2020-04-10 同济大学 Treatment method and application of antibiotic fungi residues

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337496A (en) * 2017-08-09 2017-11-10 哈尔滨工业大学 A kind of method that organic fertilizer is produced using tylosin dreg
CN110981563A (en) * 2019-12-11 2020-04-10 同济大学 Treatment method and application of antibiotic fungi residues

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙桂玲: "微波/超声波复合增强化学反应及系统研究", 《万方数据库》 *

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