CN115554645A - Method for treating antibiotic bacterial residues by hydrothermal cooperation of nZVI activated persulfate - Google Patents
Method for treating antibiotic bacterial residues by hydrothermal cooperation of nZVI activated persulfate Download PDFInfo
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Abstract
The invention belongs to the technical field of antibiotic fungi residue treatment, and discloses a method for treating antibiotic fungi residue by hydrothermal synergy of nZVI and persulfate activation. The method comprises the following steps: mixing an nZVI catalyst, persulfate and antibiotic residues, uniformly stirring into slurry to obtain a pretreated material, then placing the pretreated material into a hydrothermal reactor, heating the pretreated material in a closed environment to 80-160 ℃ for hydrothermal reaction, degrading antibiotics remained in the antibiotic residues, and hydrolyzing macromolecular organic matters into micromolecular organic matters to be dissolved in a solution phase; and (3) carrying out solid-liquid separation on the treated material to obtain a small molecular organic composite solution by using a catalyst or solid slag. According to the invention, the hydrothermal reaction is used for preparing the high-temperature and high-pressure subcritical water condition, and the subcritical water condition is cooperated with nZVI to activate persulfate, so that the degradation capability of persulfate is enhanced, the aim of deep detoxification is achieved, and the high reduction or complete liquefaction of the mushroom dregs is realized.
Description
Technical Field
The invention belongs to the technical field of antibiotic fungi residue treatment, and particularly relates to a method for treating antibiotic fungi residue by hydrothermal synergy of nZVI activated persulfate.
Background
The antibiotic fungi residues are main residual solid wastes generated in the antibiotic production process of pharmaceutical enterprises, and the main components of the antibiotic fungi residues comprise mycelium, metabolites generated in the fermentation process, an incompletely utilized culture medium, culture medium degradation products, active organic medicament adding, residual antibiotics and the like. The residual antibiotics, if untreated, tend to enter the environment and enter the body through the food chain. On the other hand, residual antibiotics may be important causes of drug resistance and resistance genes (ARGs) of germs, even produce "superbacteria", and seriously threaten the ecological environment and human health. Therefore, antibiotic residues are listed in the national records of hazardous waste (HW 02 category of medical waste).
At present, main treatment methods of antibiotic fungi residues comprise incineration, pyrolysis, composting, anaerobic digestion and the like, but the existing treatment methods still have certain limitations. The incineration is a process of burning the antibiotic bacterium residues to generate organic matters or carbon dioxide, and because the antibiotic bacterium residues have high water content and high bound water content, the mechanical dehydration method has limited effect, so that the energy loss is increased, and because the antibiotic bacterium residues have high water content and are not incinerated fully, various toxic and harmful substances such as SOx, NOx, dioxin and the like can be generated to cause secondary pollution. The pyrolysis is a technology for recovering combustible gas, biological oil or biological carbon by heating the antibiotic fungi residues at high temperature in the isolated air, is limited to the moisture content of the antibiotic fungi residues, has high energy consumption, and is easy to form precursors of hydrocyanic acid and isocyanic acid due to high nitrogen and sulfur content in the fungi residues. The composting is a method for producing the fertilizer by degrading organic matters in the antibiotic residues through microbial fermentation, and due to the inhibition effect of residual antibiotics on the microbes, the degradation effect of the antibiotics is limited, the fermentation time is long, and the treatment efficiency is low. Anaerobic digestion is a technology for producing biogas by degrading organic matters under anaerobic conditions by using facultative bacteria or anaerobic bacteria, and the method also has the limitations that mycelium is difficult to destroy, antibiotics are not thoroughly degraded and the like. In view of this, it is urgently needed to develop a green and environment-friendly method for detoxifying and reducing antibiotic residues, which has the advantages of high antibiotic degradation degree, low energy consumption, high resource utilization degree, less pollution and high treatment efficiency.
In recent years, various researchers have developed methods for treating antibiotic residues. However, the prior art represented by advanced oxidation technologies (AOPs) focuses on the decomposition of antibiotics, but ignores the Degradation of the bacterial residues themselves, so that a large amount of antibiotic residues remain after treatment, and due to adsorption, net capture and other effects, the antibiotics are easy to remain in the bacterial residues, have a certain slow-release property, and still cannot be removed from the "dangerous cap" of the bacterial residues (1) Degradation of bacterial residues from bacterial residues by activated permanent surface: degradation of antibiotic residues in biological residues and reaction [ J ] in Science of biological Environment,2022,821,153229. (2) amplification of biological activity of biological Environment in biological residues, biological activity of biological residues in biological residues, 13913913911).
The hydrothermal method is a promising harmless treatment method for antibiotic residues, and has the advantages of mild reaction conditions, small secondary pollution, high lysis rate and the like. However, the research field of hydrothermally treating antibiotic fungi residues is still in a starting stage, the process is extensive and poor in treatment effect, and the reduction and Recycling degree is low, so that the method is considered as a pretreatment method (hydrothermally treating of antibiotic fungi residues: harmless performance and resource properties [ J ], resources, conservation & Recycling,2020,161,104952 CN 109161563A, a technical method for treating and utilizing antibiotic fungi residues, CN 109628497A, a resource treatment method of antibiotic fungi residues, CN 112355034A, a Harmless pretreatment method of organic solid wastes based on Hydrothermal calcium ion blending.
Patent CN 112408685A discloses a method for removing residual antibiotics in antibiotic bacterial dreg slurry, which comprises the following steps: 1) Pretreatment: adding an acidic activating agent into the antibiotic bacteria residue slurry, and mixing to obtain activated bacteria residue slurry; 2) Oxidative degradation: adding an oxidant into the activated mushroom dreg slurry, and carrying out oxidative degradation to obtain degraded mushroom dreg slurry; 3) And (3) inactivating bacteria: sterilizing the degraded mushroom residue slurry to obtain sterilized mushroom residue slurry; 4) Neutralizing: adding an alkaline substance into the sterilized mushroom dreg slurry to obtain neutralized mushroom dreg slurry;5) And (3) post-treatment: and filtering and drying the neutralized mushroom dreg slurry to obtain a treated product. The patent adopts a specific acidic activator, an oxidant and a catalyst degradation technology, can achieve a good effect of removing residual antibiotics, but cannot realize degradation of macromolecular organic matters, reserves most organic matters for preparing a soil conditioner or an organic fertilizer, and aims at waste utilization instead of reduction. Patent CN 111170770A discloses a method for detoxifying gibberellin fermentation fungus dregs by adopting H 2 O 2 Or the hydrothermal treatment technology of the surfactant realizes the detoxification of the bacterial residues, but the degradation of macromolecular organic matters and the high reduction of the bacterial residues can not be realized.
The nanometer zero-valent iron (nZVI) is an efficient environment restoration material, can degrade various halogenated organic matters and remove heavy metal ions, and is widely applied to the environmental fields of soil and underground water restoration and the like. Patent CN 113415869A discloses a method for synergistically degrading non-degradable organic matters in town sewage by using hydrogen peroxide component in low-concentration peroxyacetic acid, adding nano zero-valent iron as a catalyst and a low-concentration peroxyacetic acid solution containing hydrogen peroxide as an oxidant into water containing antibiotics, irradiating the mixed solution with ultraviolet light emitted by a low-pressure mercury lamp, activating strong oxidative free radicals generated by the oxidant through the nano zero-valent iron and the ultraviolet light together, and synergistically degrading the non-degradable organic matters in the town sewage by the action of ultraviolet direct photolysis. Hydrogen peroxide in low-concentration peroxyacetic acid is used for cooperating with peroxyacetic acid, an nZVI catalyst is added, and ultraviolet light irradiation is carried out to construct an nZVI/UV/PAA heterogeneous strengthening system, and nZVI and UV activation are used for generating strong oxidizing free radicals to carry out oxidation removal on antibiotics. However, the patent technology is mainly used for degrading organic matters such as antibiotics in sewage, and the high reduction of the solid residues of the antibiotic fungi residues cannot be realized. Patent CN 110627250A discloses a high-grade oxidation-alkali-adjusting precipitation combined method for treating EDTA-Cu waste water. The method comprises the following steps: crushing and sieving crop straws, soaking the obtained straw powder in phosphoric acid, drying and pyrolyzing to prepare straw biochar; fully mixing the straw biochar with a ferrous sulfate solution,adding a strong reducing agent to reduce iron ions into zero-valent iron and loading the iron ions on the surface of the biochar to prepare a supported catalyst nZVI/BC; taking EDTA-Cu wastewater, adjusting the pH value, and adding Na into the reaction solution 2 S 2 O 8 After being mixed uniformly, the supported catalyst nZVI/BC is added, and after reacting for a certain time, the removal rates of EDTA-Cu and COD are respectively up to 87.8% and 72.6%, and the removal rate of heavy metals is up to 86.4%. The patent technology is mainly used for removing EDTA-Cu, COD and heavy metals in the wastewater, and can not realize high reduction of the antibiotic fungi residue solid residue.
Therefore, the development of the environment-friendly harmless treatment method for the antibiotic residues, which has the advantages of high antibiotic degradation degree, high solid residue reduction degree, low energy consumption, less pollution and high treatment efficiency and is beneficial to subsequent recycling, has obvious significance.
Disclosure of Invention
Aiming at the problems of incomplete degradation, generation of toxic substance byproducts and the like in the existing advanced oxidation technology of antibiotic residues, the invention aims to provide a method for treating antibiotic residues by hydrothermal synergy of nZVI and persulfate activation. The method has the advantages that the subcritical water condition of high temperature and high pressure is manufactured through hydrothermal reaction, and the persulfate is activated in cooperation with nZVI, so that the degradation capability of the persulfate is enhanced, on one hand, the degradation rate of antibiotics is higher, on the other hand, the generation of toxic byproducts is inhibited, the purpose of deep detoxification is achieved, the dissolution of the bacterial residues is facilitated to generate a water-soluble micromolecular organic composite solution, and the high reduction and complete liquefaction of the bacterial residues are achieved.
The purpose of the invention is realized by the following technical scheme:
a method for treating antibiotic fungi residues by activating persulfate through hydrothermal synergy of nZVI comprises the following steps:
(1) And (3) hydrothermal material blending: mixing the nZVI catalyst, persulfate and antibiotic fungi residues, and uniformly stirring to form slurry to obtain a pretreated material;
(2) Hydrothermal liquefaction: placing the pretreated material obtained in the step (1) in a hydrothermal reactor to carry out hydrothermal reaction by heating in a closed environment to 80-160 ℃;
(3) Separation: and (3) carrying out solid-liquid separation on the materials treated in the step (2) to obtain a small molecular organic composite solution by using a catalyst or solid residues.
Further, the antibiotic fungi residues in the step (1) are vancomycin fungi residues, the water content is 70-99%, and the concentration of vancomycin is 50-1500 mg/L.
Further, the nZVI catalyst in step (1) is prepared by a simple carbothermic process (carbothermic synthesis of carbon-supported nanoscale zero-valve iron composites for the differentiation of the monovalent chloride [ J ]. Environ.sci.technol.,2008,42, 2600-2605), as follows:
pulverizing corn cob, washing, drying, mixing with FeSO 4 ·7H 2 And mixing, dispersing and dissolving O in deionized water, continuously shaking for 12 hours in a shaking table, performing centrifugal separation to obtain a precipitate, and sequentially washing, freeze-drying and pyrolyzing at high temperature by using the deionized water to obtain the nZVI catalyst.
Further preferably, the dried corncobs are mixed with FeSO 4 ·7H 2 The mass ratio of the O mixture is 1.
Further preferably, the freeze drying refers to vacuum drying at-60 ℃ for 24h; the high-temperature pyrolysis refers to pyrolysis at 600 ℃ for 2h.
Further, the dry weight ratio of the nZVI catalyst to the antibiotic fungi residues in the step (1) is 0.01-0.5, preferably 0.2; the dry weight ratio of the persulfate to the antibiotic fungi residues is 0.01-0.5, preferably 0.2.
Further preferably, the persulfate is potassium persulfate.
Further, the water content of the pretreated material in the step (1) is controlled to be 80-95%, and preferably 85%.
Further, the time of the hydrothermal reaction in the step (2) is 30-360 min.
Further preferably, the hydrothermal reaction temperature in the step (2) is 120 ℃ and the hydrothermal reaction time is 90min.
Further, the solid-liquid separation method in the step (3) includes centrifugation, suction filtration or filter pressing.
Further, the decrement rate of the solid slag obtained in the step (3) is 84.3-100%. The decrement rate calculation method comprises the following steps: taking 10mL of mixed post-treatment sample, filtering the sample through a 0.22-micron organic filter membrane to obtain filter residue, drying the filter residue in vacuum for 8 hours, weighing the dried sludge mass by using a balance, wherein the conversion unit is g/100mL and is recorded as m 2 ，
Further, the small molecule organic composite solution obtained in the step (3) is used for preparing a culture medium carbon source or carrying out anaerobic digestion to produce methane.
The principle of the invention is as follows:
according to the invention, the hydrothermal high-temperature and high-pressure condition is utilized to destroy the mycelium structure in the antibiotic fungi residues, so that the cell membrane structure is promoted to break, the combined water and intracellular water are removed, the wet antibiotic fungi residues can be directly treated, and an additional dehydration process is not needed; the subcritical water condition of hydrothermal production is favorable for the organic reaction; and the hydrothermal high-temperature and high-pressure condition can also excite persulfate, and the persulfate is further activated by cooperating with the catalysis of nZVI, so that residual antibiotics are efficiently degraded, and the hydrolysis of macromolecular organic matters into micromolecular organic matters is efficiently promoted to be dissolved in a solution phase, and the complete liquefaction or high reduction of antibiotic residues is realized. The detoxified small molecular organic composite solution can be further used for preparing a culture medium carbon source or carrying out anaerobic digestion to produce methane.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method solves the problems of incomplete antibiotic degradation, severe conditions, high energy consumption, difficult resource recycling, serious resource waste and the like in the traditional antibiotic residue hydrothermal treatment technology; the aims of thorough detoxification, complete liquefaction and high-efficiency recycling of antibiotic fungi residues are achieved.
(2) The micromolecule organic composite solution obtained by the invention can be further prepared into a culture medium carbon source or subjected to anaerobic digestion to generate methane, the recycling degree is high, the cap removal of hazardous wastes is finally realized, and the micromolecule organic composite solution has wide application prospect and important environmental significance.
Drawings
FIG. 1 is a HPLC chromatogram of a vancomycin standard sample and HPLC detection results of vancomycin in the small molecule organic composite solution obtained in examples 1 to 3.
FIG. 2 is a diagram showing HPLC detection results of vancomycin in the composite solutions obtained in comparative examples 1 to 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The nZVI catalysts used in the following examples were prepared by carbothermic reduction: selecting corn cob as raw material of biochar, pulverizing at 60 deg.C, washing, drying for 24 hr, weighing 1g treated corn cob, and 4.9643g FeSO 4 ·7H 2 Mixing and dissolving O in 50mL of deionized water, continuously shaking the mixture in a shaking table for 12 hours, performing centrifugal separation to obtain a precipitate, washing the precipitate with the deionized water for three times to remove redundant iron, performing vacuum drying at the temperature of-60 ℃ for 24 hours, and performing pyrolysis at the temperature of 600 ℃ for 2 hours by using a muffle furnace to obtain the nZVI catalyst.
Example 1
The method for treating antibiotic fungi residues by hydrothermal cooperation of nZVI and persulfate activation comprises the following steps:
(1) And (3) hydrothermal material blending: mixing nZVI catalyst, potassium persulfate and pasty vancomycin bacterial slag to be treated (the water content is 95.4%, the concentration of vancomycin is 260.818mg/L, and the mass of dry-basis sludge is m 1 =4.89g/100mL (i.e. 100mL of the bacterial residue was filtered through a 0.22 μm organic filter membrane to obtain a filter residue, the filter residue was dried in vacuum for 8h, and the mass of the dried sludge was weighed using a balance and recorded as m 1 ) Mixing, wherein the dry weight ratio of the nZVI catalyst to the antibiotic fungi residues is 0.2.
(2) Hydrothermal liquefaction: and (2) placing the pretreated material obtained in the step (1) in a hydrothermal reactor, heating the pretreated material in a closed environment to 120 ℃, carrying out hydrothermal reaction for 90min, degrading antibiotics remained in the antibiotic fungi residues, and hydrolyzing macromolecular organic matters into micromolecular organic matters to be dissolved in a solution phase.
(3) Separation: and (3) carrying out suction filtration separation on the material treated in the step (2) to recover the catalyst, thereby obtaining a completely dissolved small molecular organic composite solution.
The solid waste reduction rate of this example was 100%. The HPLC detection result of vancomycin in the obtained small molecule organic complex solution by the method described in USP dictionary is shown in FIG. 1. As can be seen from the results in FIG. 1, vancomycin was not detected in the small molecule organic complex solution, which indicates that the treatment method of this example was used to completely degrade antibiotics.
The micromolecule organic composite solution obtained in the embodiment is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 5.01L/d.
Example 2
The method for treating antibiotic fungi residues by using hydrothermal cooperation of nZVI and persulfate activation comprises the following steps:
(1) Hydrothermal material blending: mixing the nZVI catalyst, potassium persulfate and pasty vancomycin bacterial slag to be treated (the water content is 95.4 percent, the concentration of vancomycin is 260.818mg/L, and the mass of dry-based sludge is m 1 =4.89g/100 mL), wherein the dry weight ratio of the nZVI catalyst to the antibiotic fungi residues is 0.5.
(2) Hydrothermal liquefaction: and (2) placing the pretreated material obtained in the step (1) in a hydrothermal reactor, heating the pretreated material in a closed environment to 80 ℃, carrying out hydrothermal reaction for 360min to degrade antibiotics remained in the antibiotic fungi residues, and hydrolyzing the macromolecular organic matters into micromolecular organic matters to be dissolved in a solution phase.
(3) Separation: centrifuging the material treated in the step (2) at 8000rpm to obtain reduced solid slag and a small molecular organic composite solution.
The solid waste reduction rate of this example was 84.3%. The HPLC detection result of vancomycin in the obtained small molecule organic complex solution by the method described in USP dictionary is shown in FIG. 1. As can be seen from the results in FIG. 1, no vancomycin was detected in the small molecule organic complex solution, indicating that the antibiotic was completely degraded by the treatment method of this example.
The micromolecule organic composite solution obtained in the embodiment is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 5.24L/d.
Example 3
The method for treating antibiotic fungi residues by using hydrothermal cooperation of nZVI and persulfate activation comprises the following steps:
(1) Hydrothermal material blending: mixing nZVI catalyst, potassium persulfate and pasty vancomycin bacterial slag (the water content is 95.4%, the vancomycin concentration is 260.818mg/L, and the mass of dry sludge is m 1 =4.89g/100 mL), wherein the dry weight ratio of the nZVI catalyst to the antibiotic fungi residues is 0.1.
(2) Hydrothermal liquefaction: and (2) placing the pretreated material obtained in the step (1) in a hydrothermal reactor, heating the pretreated material in a closed environment to 160 ℃, carrying out hydrothermal reaction for 120min, degrading antibiotics remained in the antibiotic fungi residues, and hydrolyzing the macromolecular organic matters into micromolecular organic matters to be dissolved in a solution phase.
(3) Separation: and (3) carrying out suction filtration separation on the materials treated in the step (2) to recover the catalyst, thereby obtaining the reduced solid slag and the small molecular organic composite solution.
The solid waste reduction rate of this example was 98.9%. The HPLC detection result of vancomycin in the obtained small molecule organic complex solution by the method described in USP dictionary is shown in FIG. 1. As can be seen from the results in FIG. 1, no vancomycin was detected in the small molecule organic complex solution, indicating that the antibiotic was completely degraded by the treatment method of this example.
The micromolecule organic composite solution obtained in the embodiment is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 4.88L/d.
Comparative example 1
This comparative example compares to example 1 without the addition of the nZVI catalyst, the rest being identical.
The solid waste reduction rate of this comparative example was 80.3%. The HPLC detection result of vancomycin in the obtained small molecule organic complex solution by the method described in USP dictionary is shown in FIG. 2. As can be seen from the results in FIG. 2, no vancomycin was detected in the small molecule organic complex solution, indicating that the antibiotics were completely degraded by the treatment method of this comparative example.
The micromolecule organic composite solution obtained in the comparative example is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 4.46L/d.
As can be seen from comparison between the comparative example 1 and the example 1, the invention adopts the water man to cooperate with the catalysis of the nZVI to further activate the persulfate, so as to realize the complete liquefaction of the antibiotic residues.
Comparative example 2
This comparative example compares to example 1, no potassium persulfate was added, and the rest is the same.
The solid waste reduction rate of this comparative example was 50.4%. The HPLC detection result of vancomycin in the obtained small molecule organic complex solution by the method described in USP dictionary is shown in FIG. 2. As can be seen from the results in FIG. 2, the vancomycin concentration was 23.448mg/L.
The micromolecule organic composite solution obtained in the comparative example is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 0.40L/d.
Comparative example 3
Compared with the embodiment 1, the comparative example adopts normal temperature stirring reaction to replace high temperature hydrothermal reaction, and the rest is the same.
The solid waste reduction rate of this comparative example was 30.2%. The HPLC detection result of vancomycin in the obtained small molecule organic composite solution is shown in figure 2 by the method described in USP dictionary. As can be seen from the results in FIG. 2, the vancomycin concentration is 89.665mg/L.
The micromolecule organic composite solution obtained in the comparative example is subjected to anaerobic digestion in a simple SBR reactor, and the methane yield is 0.07L/d.
As can be seen from comparison of comparative examples 1-3 and example 1, the method can significantly promote deep detoxification and high reduction of the bacterial residues through the synergistic effect of hydrothermal reaction, nZVI catalysis and persulfate oxidation. The detoxified and degraded small molecular organic composite solution can be subjected to anaerobic digestion to generate methane with higher efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for treating antibiotic fungi residues by activating persulfate through hydrothermal synergy of nZVI is characterized by comprising the following steps:
(1) And (3) hydrothermal material blending: mixing the nZVI catalyst, persulfate and antibiotic residues, and uniformly stirring to form slurry to obtain a pretreated material;
(2) Hydrothermal liquefaction: placing the pretreated material obtained in the step (1) in a hydrothermal reactor to carry out hydrothermal reaction by heating in a closed environment to 80-160 ℃;
(3) Separation: and (3) carrying out solid-liquid separation on the materials treated in the step (2) to obtain a catalyst or solid slag to obtain a micromolecule organic composite solution.
2. The method for treating antibiotic fungi residues through hydrothermal synergism of nZVI activated persulfate as claimed in claim 1, wherein the antibiotic fungi residues in the step (1) are vancomycin fungi residues, the water content is 70% -99%, and the concentration of vancomycin is 50-1500 mg/L.
3. The method for treating antibiotic residues by hydrothermal synergy of nZVI activated persulfate according to claim 1, characterized in that the nZVI catalyst in the step (1) is prepared by the following method:
pulverizing corn cob, washing, drying, mixing with FeSO 4 ·7H 2 And mixing, dispersing and dissolving O in deionized water, continuously shaking for 12 hours in a shaking table, performing centrifugal separation to obtain a precipitate, and sequentially washing the precipitate with deionized water, freeze-drying and pyrolyzing at high temperature to obtain the nZVI catalyst.
4. The method for treating antibiotic residues by hydrothermal synergy of nZVI activated persulfate according to claim 1, wherein the dry weight ratio of the nZVI catalyst to the antibiotic residues in the step (1) is 0.01-0.5; the dry weight ratio of the persulfate to the antibiotic fungi residues is 0.01-0.5.
5. The method for treating antibiotic residues by the hydrothermal synergism of nZVI activated persulfate according to claim 5, wherein the persulfate is potassium persulfate.
6. The method for treating antibiotic residues by hydrothermal synergy of nZVI activated persulfate according to claim 1, wherein the water content of the pretreated material in the step (1) is controlled to be 80-95%.
7. The method for treating antibiotic fungi residues by hydrothermal synergy of nZVI and persulfate, as claimed in claim 1, wherein the hydrothermal reaction time in step (2) is 30-360 min.
8. The method for treating antibiotic residues by hydrothermal synergy of nZVI activated persulfate according to claim 8, wherein the hydrothermal reaction temperature in the step (2) is 120 ℃, and the hydrothermal reaction time is 90min.
9. The method for treating antibiotic fungi residues by hydrothermal synergy of nZVI and persulfate activation according to claim 1, wherein the solid-liquid separation method in the step (3) comprises centrifugation, suction filtration or pressure filtration.
10. The method for treating antibiotic residues by hydrothermal synergism of nZVI activated persulfate according to claim 1, wherein the small molecule organic complex solution obtained in the step (3) is used for preparing a culture medium carbon source or is subjected to anaerobic digestion to produce methane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000218295A (en) * | 1999-02-01 | 2000-08-08 | Sadaaki Murakami | Surplus sludge zero emission type biological treating method using hydrothermal reaction |
| CN103721715A (en) * | 2013-11-28 | 2014-04-16 | 温州大学 | Activated charcoal loaded nano zero-valent iron material |
| CN107365593A (en) * | 2017-09-07 | 2017-11-21 | 中国科学院城市环境研究所 | A kind of method that antibiotic bacterium dregs prepare charcoal |
| CN109628497A (en) * | 2018-12-10 | 2019-04-16 | 河北科技大学 | A kind of antibiotic bacterium dregs recycling processing method |
| CN112934932A (en) * | 2021-04-14 | 2021-06-11 | 同济大学 | Harmless treatment method for antibiotic mushroom dregs |
-
2022
- 2022-09-27 CN CN202211184351.3A patent/CN115554645B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000218295A (en) * | 1999-02-01 | 2000-08-08 | Sadaaki Murakami | Surplus sludge zero emission type biological treating method using hydrothermal reaction |
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| CN115672951A (en) * | 2022-09-27 | 2023-02-03 | 中南大学 | Efficient harmless treatment method for antibiotic fungi residues |
| CN115672951B (en) * | 2022-09-27 | 2024-06-28 | 中南大学 | Efficient harmless treatment method for antibiotic fungus residues |
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