CN106422152A - Method for removing oxytetracycline in biological medicine waste residues - Google Patents
Method for removing oxytetracycline in biological medicine waste residues Download PDFInfo
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract
The invention relates to a method for removing oxytetracycline in biological medicine waste residues. The steps of pretreatment, catalytic oxydative degradation, bacterium inactivation, neutralizing treatment and the like are adopted, and an organic matter waste residue product containing no oxytetracycline can be formed after drying and can be used for preparing subsequent soil conditioners and organic and inorganic compound fertilizer. Compared with the prior art, purchase, use and management are easy, and hydrogen peroxide is convenient to use; and the method is used for treating the biological medicine waste residues, the oxytetracycline waste residue cost is low, the treatment process is fast, environment-friendly and small in harm, finally, the biological medicine waste residues are used as raw materials of the organic fertilizer or the soil conditioners, and the utilization value is high.
Description
Technical field
The invention belongs to medical environmental technology field, especially relate to a kind of side removing terramycin in biological medicine waste residue
Method.
Background technology
China is antibiotic production of raw medicine the biggest in the world and big export country, produces more than 70 kinds of antibiotic, accounts for the whole world
The 70% of production.According to 8～10 tons of bacteria residue estimations of antibiotics production per ton, generation millions of tons is contained resist on a small quantity every year
The bacteria residue of raw element.
Contain a small amount of antibiotic and its degradation product due in the useless bacteria residue of antibiotic fermentation, there is to ecological environment potential danger
Evil, has become one of internationally recognized public hazards.If the supervision of enterprise and environmental administration not in place it is possible to make antibiosis
Plain bacteria residue, without harmlessness disposing, flows directly into animal feed or organic fertilizer market, and the antibiotic of wherein residual is not only right
Ecological environment produces impact, produces harm to health after also being enriched with by food chain.
The department such as the Ministry of Agriculture of China, Ministry of Public Health combines issue within 2002《Forbid using in feed and animal drinking water
Types of drugs catalogue》, antibiotic filter residue is listed in catalogue.2008 revised《National Hazard waste register》It is expressly recited
" mother liquor during chemicals production of raw medicine and reactive group or culture medium waste " is HW02 clinical waste, should be according to medical treatment
Hazardous waste carries out safe disposal, and this regulation further limit antibiotic bacterium dregs and processes as feed addictive, organic fertilizer
Treatment approach.
At present biological medicine terramycin waste residue innoxious process for treating method is had in physico-chemical process, catalysis oxidation
Method, photocatalytic method, absorption etc. are the important method removing the antibiotic such as terramycin, and they are mostly degradable or improve its biology fall
Xie Xing.Wherein catalytic oxidation includes O3 catalytic oxidation, Fenton reagent homogeneous catalytic oxidation etc., and O3 catalytic oxidation method is
By adding Mn in system2+-MnO2Deng catalyst, in the presence of catalyst, make ozone molecule formed as hydroxyl radical free radical,
The Strong oxdiative group such as Both peroxyl radical, oxidative degradation antibiotic, the oxidation of its antibiotic is cleared up rate and can be reached 75～96%.
Also have Fenton-like method, that is, pass through the medicaments such as interpolation methyl alcohol, calcium oxide and improve antibiotic oxidation effectiveness further.According to document report
Road, the research such as Sun Hongli is reacted under certain condition and can be made terramycin in the dregs of a decoction by adding hydrochloric acid, methyl alcohol and calcium oxide
Clearance reaches 96.9%.Wang Chun equality research adopts Fenton reagent-lime method to process terramycin residue, and its clearance reaches
More than 87%.The research such as Li Kuixiao is processed using Fenton reagent and contains terramycin wastewater, and its terramycin clearance reaches 92.5%.
Also have using with the δ-MnO of chemical synthesis2For oxidant, antibiotic is carried out with oxidative degradation, and the light source in specific wavelength
Irradiate lower generation catalytic action, make the water in environment and oxygen excite formation OH and O-2Free radical.Catalyst has TiO2、
ZnO、Fe3O4Deng.
Chinese patent CN101176511B discloses the method removing or reducing the left drug composition in Terramycin-type waste water,
Comprise the steps：The dregs of a decoction are dissolved by A, acid solution, make the active ingredient release remaining in the medicine in mycelia be dissolved in solution
In；B, stirring under conditions of heating response, make release left drug be destroyed；Adding in C, reactant liquor after the heating has
Machine solvent, makes to remain in the residual potency dissolving in mycelia further；D, it is filtered to remove solution, the filter residue calcium hydroxide obtaining
Or calcium oxide adjusts pH value 6.5-7.0, it is dried after making particle, need in this patent to add organic solvent, rely on organic solvent
The drug titers of dissolving residual, still contain residual terramycin after treatment in addition it is also necessary to process again in solution.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide a kind of operating procedure simple,
Economical and practical, terramycin fast degradation being used for safety index in biological medicine waste residue can be removed biological medicine and give up
The method of terramycin in slag.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method removing terramycin in biological medicine waste residue is it is characterised in that adopt following steps：
(1) pre-process：Pending biological medicine waste residue containing terramycin is mixed with water, through sizing mixing, disperseing, makes solid
Content is the waste residue slurries of 5-30wt%；
(2) catalyzing oxidizing degrading：
(2-1) pH value of adjustment waste residue slurries is to 1.0-2.0；
(2-2) oxidation catalysis medicament is added to carry out catalyzing oxidizing degrading；
(3) bacteria inactivation：Waste residue slurries after oxidative degradation are carried out sterilization treatment；
(4) neutralize：Waste residue after sterilization treatment is neutralized process, can form the organic matter without antibiotic after being dried
Waste residue product, can be used for the preparation of follow-up soil conditioner, compound organic and inorganic fertilizer.
The pH value of the adjustment waste residue slurry system described in step (2-1), the wherein former pH value of waste residue slurries are 5.0-6.0, institute
The acid of adjustment pH value is sulfuric acid, and pH final value to be adjusted is 1.0-2.0.
Oxidant in the oxidation catalysis medicament adding in step (2-2) with the mass ratio of pending biological medicine waste residue is
1:10～1000.
The oxidation catalysis medicament adding in step (2-2) is 1 by catalyst and oxidant in mass ratio:1～10 mixes
Arrive.
Described catalyst is sulfate or hydrochloride.
Preferably, can be using ferrous sulfate, cobaltous sulfate or frerrous chloride.
More preferred, catalyst adopts FeSO4·7H2O.
Described oxidant is hydrogen peroxide, ozone or sodium hypochlorite etc. it is contemplated that stability, oxidation efficiency and preparation
Convenience, preferably hydrogen peroxide.
The temperature that step (2-2) carries out catalyzing oxidizing degrading is 10 DEG C～140 DEG C, pressure is 0～0.5Mpa, the time is
0.5～8 hour.
Step (3) carry out during bacteria inactivation control pressure be 0～0.5Mpa, temperature be 100～130 DEG C, the time be 20～
80 minutes.
The pH value of waste residue is adjusted and is neutralized process to 5～6 by step (4).
Compared with prior art, the present invention adopts catalytic oxidation treatment sterilizing integrated technology, mould to the soil of residual in waste residue
Element is removed, because in acid condition, residual terramycin is completely dissolved, and oxidation reaction is carried out in homogeneous phase condition, peroxidating
Hydrogen is in Fe2+There is under the catalytic condition of ion higher oxidation-reduction potential, bright to the oxidation of group effective in terramycin
Aobvious, therefore, there is higher clearance, and secondary pollution product will not be produced, belong to harmless treatment, detailed process includes pre-
Process, catalyzing oxidizing degrading, filtration separation, drying etc., products obtained therefrom can be used for preparing soil conditioner or organic-inorganic compound
Fertilizer, realizes clean manufacturing and resource, the beneficial environmental properties recycling, has good environmental protection application prospect.The inventive method
The terramycin that can be 4000ppm-6000ppm by the concentration of residual in original waste residue is rapidly reduced to 0-30ppm, and medicine dregs
Rate of mass reduction be less than 10%, there is good application prospect.
Terramycin will be remained using oxidant under certain catalytic condition in the application to decompose, it is to avoid remain in waste liquid
The process again of terramycin, the dregs of a decoction after treatment can use directly as the raw material of soil conditioner, composite organic-inorganic fertilizer,
And meet environmental requirement.
Because Terramycin-type waste water itself is in acidity, therefore can be directly dissolved in water and carry out catalytic oxidation.Sterilizing
The technological parameter processing is contained in the technological parameter of catalyzing oxidizing degrading, produces impact thus without on final result.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Process terramycin waste residue 30g, terramycin content 5656mg/L.Adding water sizes mixing forms the slurries of solid content 20%, and
System pH is modulated 1.2 to by sulfuric acid.Under 100 DEG C, condition of normal pressure, add oxidant H2O20.3g, catalyst Fe SO4·
7H2O 0.1g, aoxidizes 2 hours.Put into 120 DEG C after the completion of reaction, sterilize 20 minutes in steam sterilization pan under the conditions of 0.5Mpa.With
Adjusting system pH by NaOH afterwards is 5.5, through filtering and being dried, obtains the product 35g that solid content is 80%；After testing
Oxytetracycline residues are 40ppm, and degradation rate reaches more than 99%.
Embodiment 2
Process terramycin waste residue 100g, terramycin content 5235mg/L.Adding water sizes mixing forms the slurries of solid content 10%, and
System pH is modulated 1.5 to by sulfuric acid.Under 85 DEG C, condition of normal pressure, add oxidant H2O20.3g, catalyst Fe SO4·
7H2O 0.06g, aoxidizes 3.5 hours.Put into 110 DEG C after the completion of reaction, sterilize 40 points in steam sterilization pan under the conditions of 0.2Mpa
Clock.Subsequently adjusting system pH by potassium hydroxide is 5.6, through filtering and being dried, obtains the product 125g that solid content is 78%；
Oxytetracycline residues are 0.5ppm after testing, and degradation rate reaches more than 99%.
Embodiment 3
Process terramycin waste residue 310g, terramycin content 5100mg/L.Adding water sizes mixing forms the slurries of solid content 12%, and
System pH is modulated 1.0 to by sulfuric acid.Under 140 DEG C, 0.4Mpa pressure condition, add oxidant H2O20.5g, catalyst
FeSO4·7H2O 0.5g, aoxidizes 0.5 hour.Put into 130 DEG C after the completion of reaction, sterilize 30 in steam sterilization pan under the conditions of 0.4Mpa
Minute.Subsequently adjusting system pH by calcium hydroxide is 6.0, through filtering and being dried, obtains the product that solid content is 75%
416g；Oxytetracycline residues are 15ppm after testing, and degradation rate reaches more than 99%.
Embodiment 4
Process terramycin waste residue 700g, terramycin content 5360mg/L.Adding water sizes mixing forms the slurries of solid content 5%, and
System pH is modulated 1.5 to by sulfuric acid.Under 50 DEG C, 0.2Mpa pressure condition, add oxidant H2O20.7g, catalyst
FeSO4·7H2O 0.35g, aoxidizes 5 hours.Put into 105 DEG C after the completion of reaction, sterilize 80 in steam sterilization pan under the conditions of 0.5Mpa
Minute.Subsequently adjusting system pH by potassium hydroxide is 5.0, through filtering and being dried, obtains the product that solid content is 70%
980g；Oxytetracycline residues are 23ppm after testing, and degradation rate reaches more than 99%.
Embodiment 5
Process terramycin waste residue 1200g, terramycin content 4735mg/L.Adding water sizes mixing forms the slurries of solid content 30%,
And system pH is modulated 1.6 to by sulfuric acid.Under 10 DEG C, 0.1Mpa pressure condition, add oxidant H2O22.7g, catalyst
FeSO4·7H2O 0.27g, aoxidizes 8 hours.Put into 125 DEG C after the completion of reaction, sterilize 50 in steam sterilization pan under the conditions of 0.3Mpa
Minute.Subsequently adjusting system pH by NaOH is 5.5, through filtering and being dried, obtains the product that solid content is 75%
1550g；Oxytetracycline residues are 43ppm after testing, and degradation rate reaches more than 99%.
Embodiment 6
Process terramycin waste residue 2100g, terramycin content 4969mg/L.Adding water sizes mixing forms the slurries of solid content 15%,
And system pH is modulated 1.0 to by sulfuric acid.Under 30 DEG C, condition of normal pressure, add oxidant H2O22.62g, catalyst Fe SO4·
7H2O 0.33g, aoxidizes 7 hours.Put into 100 DEG C after the completion of reaction, sterilize 10 minutes in steam sterilization pan under the conditions of 0.1Mpa.
Subsequently adjusting system pH by calcium hydroxide is 5.6, through filtering and being dried, obtains the product 2550g that solid content is 80%；Warp
Detection oxytetracycline residues are 26ppm, and degradation rate reaches more than 99%.
Embodiment 7
Process terramycin waste residue 3000g, terramycin content 4800mg/L.Adding water sizes mixing forms the slurries of solid content 25%,
And system pH is modulated 2.0 to by sulfuric acid.Under 30 DEG C, condition of normal pressure, add oxidant H2O220g, catalyst Fe SO4·
7H2O 5g, aoxidizes 1 hour.Put into 115 DEG C after the completion of reaction, sterilize 60 minutes in steam sterilization pan under the conditions of 0.4Mpa.Subsequently
It is 6.0 by NaOH adjustment system pH, through filtering and being dried, obtain the product 3840g that solid content is 75%；After testing
Oxytetracycline residues are 18ppm, and degradation rate reaches more than 99%.
Embodiment 8
Process terramycin waste residue 4500g, terramycin content 5890mg/L.Adding water sizes mixing forms the slurries of solid content 18%,
And system pH is modulated 1.2 to by sulfuric acid.Under 70 DEG C, condition of normal pressure, add oxidant H2O25g, catalyst Fe SO4·
7H2O 0.83g, aoxidizes 3 hours.Put into 128 DEG C after the completion of reaction, sterilize 15 minutes in steam sterilization pan under the conditions of 0.3Mpa.
Subsequently adjusting system pH by potassium hydroxide is 5.2, through filtering and being dried, obtains the product 5560g that solid content is 78%；Warp
Detection oxytetracycline residues are 45ppm, and degradation rate reaches more than 99%.
Embodiment 9
Process terramycin waste residue 5200g, terramycin content 4980mg/L.Adding water sizes mixing forms the slurries of solid content 27%,
And system pH is modulated 1.5 to by sulfuric acid.Under 90 DEG C, condition of normal pressure, add oxidant H2O25.8g, catalyst Fe SO4·
7H2O 1g, aoxidizes 4 hours.Put into 112 DEG C after the completion of reaction, sterilize 55 minutes in steam sterilization pan under the conditions of 0.5Mpa.Subsequently
It is 6.0 by calcium hydroxide adjustment system pH, through filtering and being dried, obtain the product 6860g that solid content is 75%；After testing
Oxytetracycline residues are 36ppm, and degradation rate reaches more than 99%.
Embodiment 10
Process terramycin waste residue 6700g, terramycin content 4850mg/L.Adding water sizes mixing forms the slurries of solid content 8%, and
System pH is modulated 2.0 to by sulfuric acid.Under 90 DEG C, condition of normal pressure, add oxidant H2O210g, catalyst Fe SO4·7H2O
1.5g, aoxidizes 6 hours.Put into 108 DEG C after the completion of reaction, sterilize 35 minutes in steam sterilization pan under the conditions of 0.4Mpa.Subsequently by
NaOH adjustment system pH is 5.0, through filtering and being dried, obtains the product 8200g that solid content is 80%；Soil after testing
Mycin residual quantity is 29ppm, and degradation rate reaches more than 99%.
Embodiment 11
A kind of method removing terramycin in biological medicine waste residue is it is characterised in that adopt following steps：
(1) pre-process：Pending biological medicine waste residue containing terramycin is mixed with water, through sizing mixing, disperseing, makes solid
Content is the waste residue slurries of 5wt%, and pH value is 5.0；
(2) catalyzing oxidizing degrading：
(2-1) sulfuric acid is utilized to adjust the pH value of waste residue slurries to 1.0；
(2-2) oxidation catalysis medicament is added to carry out catalyzing oxidizing degrading, oxidation catalysis medicament therein is by catalyst sulfuric acid
Cobalt and oxidizing agent sodium hypochlorite are 1 in mass ratio:1 is mixed to get, the mass ratio of sodium hypochlorite and pending biological medicine waste residue
For 1:10, the temperature of catalyzing oxidizing degrading is 10 DEG C, pressure is 0Mpa, the time is 8 hours；
(3) bacteria inactivation：Waste residue slurries after oxidative degradation are carried out sterilization treatment, during bacteria inactivation, control pressure is
0Mpa, temperature are 130 DEG C, the time is 80 minutes；
(4) neutralize：The pH value of the waste residue after sterilization treatment is adjusted and is neutralized process to 5, can be formed not after being dried
Organic matter waste residue product containing antibiotic, can be used for the preparation of follow-up soil conditioner, compound organic and inorganic fertilizer.
Embodiment 12
A kind of method removing terramycin in biological medicine waste residue is it is characterised in that adopt following steps：
(1) pre-process：Pending biological medicine waste residue containing terramycin is mixed with water, through sizing mixing, disperseing, makes solid
Content is the waste residue slurries of 30wt%, and pH value is 6.0；
(2) catalyzing oxidizing degrading：
(2-1) sulfuric acid is utilized to adjust the pH value of waste residue slurries to 2.0；
(2-2) oxidation catalysis medicament is added to carry out catalyzing oxidizing degrading, oxidation catalysis medicament therein is by catalyst chlorination
Ferrous is 1 with oxidant, ozone in mass ratio:10 are mixed to get, and ozone is 1 with the mass ratio of pending biological medicine waste residue:
1000, the temperature of catalyzing oxidizing degrading is 140 DEG C, pressure is 0.5Mpa, the time is 0.5 hour；
(3) bacteria inactivation：Waste residue slurries after oxidative degradation are carried out sterilization treatment, during bacteria inactivation, control pressure is
0.5Mpa, temperature are 100 DEG C, the time is 20 minutes；
(4) neutralize：The pH value of the waste residue after sterilization treatment is adjusted and is neutralized process to 6, can be formed not after being dried
Organic matter waste residue product containing antibiotic, can be used for the preparation of follow-up soil conditioner, compound organic and inorganic fertilizer.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel
Within protection domain.
Claims (10)
1. a kind of method removing terramycin in biological medicine waste residue is it is characterised in that adopt following steps：
(1) pre-process：Pending biological medicine waste residue containing terramycin is mixed with water, through sizing mixing, disperseing, makes solid content
Waste residue slurries for 5-30wt%；
(2) catalyzing oxidizing degrading：
(2-1) pH value of adjustment waste residue slurries is to 1.0-2.0；
(2-2) oxidation catalysis medicament is added to carry out catalyzing oxidizing degrading；
(3) bacteria inactivation：Waste residue slurries after oxidative degradation are carried out sterilization treatment；
(4) neutralize：Waste residue after sterilization treatment is neutralized process, last re-dry.
2. a kind of method removing terramycin in biological medicine waste residue according to claim 1 is it is characterised in that step
(2-2) oxidant in the oxidation catalysis medicament adding in is 1 with the mass ratio of pending biological medicine waste residue:10～1000.
3. a kind of method removing terramycin in biological medicine waste residue according to claim 1 and 2 is it is characterised in that walk
Suddenly the oxidation catalysis medicament adding in (2-2) is 1 by catalyst and oxidant in mass ratio:1～10 is mixed to get.
4. a kind of method removing terramycin in biological medicine waste residue according to claim 3 is it is characterised in that described
Catalyst is sulfate or hydrochloride.
5. a kind of method removing terramycin in biological medicine waste residue according to claim 4 is it is characterised in that described
Catalyst includes ferrous sulfate, cobaltous sulfate or frerrous chloride, preferably FeSO4·7H2O.
6. a kind of method removing terramycin in biological medicine waste residue according to claim 3 is it is characterised in that described
Oxidant is hydrogen peroxide, ozone or sodium hypochlorite.
7. a kind of method removing terramycin in biological medicine waste residue according to claim 3 is it is characterised in that described
The preferred hydrogen peroxide of oxidant.
8. a kind of method removing terramycin in biological medicine waste residue according to claim 1 and 2 is it is characterised in that walk
Suddenly the temperature that (2-2) carries out catalyzing oxidizing degrading is 10 DEG C～140 DEG C, pressure is 0～0.5Mpa, the time is 0.5～8 hour.
9. a kind of method removing terramycin in biological medicine waste residue according to claim 1 is it is characterised in that step
(3) carry out during bacteria inactivation control pressure be 0～0.5Mpa, temperature be 100～130 DEG C, the time be 20～80 minutes.
10. a kind of method removing terramycin in biological medicine waste residue according to claim 1 is it is characterised in that step
(4) pH value of waste residue is adjusted and be neutralized process to 5～6.
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| CN107311729A (en) * | 2017-08-04 | 2017-11-03 | 哈尔滨工业大学 | A kind of method that utilization lincomycin fungi residues produce organic fertilizer |
| CN107324905A (en) * | 2017-08-04 | 2017-11-07 | 哈尔滨工业大学 | A kind of method that utilization erythromycin bacterium slag produces organic fertilizer |
| 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 |
| CN107353114A (en) * | 2017-08-09 | 2017-11-17 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue |
| CN107337497A (en) * | 2017-08-11 | 2017-11-10 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using aminoglycoside antibiotics bacteria residue |
| CN107382419A (en) * | 2017-08-11 | 2017-11-24 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using macrolide antibiotic bacterium dregs |
| CN107522546A (en) * | 2017-08-30 | 2017-12-29 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using polypeptide antibiotics bacteria residue |
| CN107500984A (en) * | 2017-09-21 | 2017-12-22 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using Fenton process processing antibiotic bacterium dregs |
| CN107497849A (en) * | 2017-10-10 | 2017-12-22 | 吴洪生 | The in situ of pedo relict antibiotic/agricultural chemicals eliminates recovery technique and application |
| CN108260709A (en) * | 2018-01-10 | 2018-07-10 | 宁夏大学 | A kind of biodegrading process of biofermentation tetracycline dregs of a decoction and its application |
| CN108653971A (en) * | 2018-03-27 | 2018-10-16 | 上海化工研究院有限公司 | A method of remaining penicillin antibiotics in removal biological medicine waste residue |
| CN110338280A (en) * | 2019-07-09 | 2019-10-18 | 中国水产科学研究院珠江水产研究所 | A kind of medicinal fish feed that can reduce antibiotic residue |
| CN110592067A (en) * | 2019-09-20 | 2019-12-20 | 广东省农业科学院农业资源与环境研究所 | In-situ microorganism repairing agent for tetracycline antibiotic contaminated soil, preparation method and application |
| CN111635262A (en) * | 2020-06-05 | 2020-09-08 | 北京紫光英力化工技术有限公司 | Degradation method of livestock and poultry manure antibiotic |
| CN112408685A (en) * | 2020-11-25 | 2021-02-26 | 上海化工研究院有限公司 | Method for removing residual antibiotics in antibiotic dreg slurry |
| CN114380647A (en) * | 2021-12-09 | 2022-04-22 | 上海化工研究院有限公司 | Method for preparing organic fertilizer by materializing traditional Chinese medicine residues |
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