CN107353114A - A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue - Google Patents
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue Download PDFInfo
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- CN107353114A CN107353114A CN201710675894.8A CN201710675894A CN107353114A CN 107353114 A CN107353114 A CN 107353114A CN 201710675894 A CN201710675894 A CN 201710675894A CN 107353114 A CN107353114 A CN 107353114A
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- bacteria residue
- tetracycline antibiotics
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
Abstract
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue, it is related to harmless treatment and the resource utilization method of tetracycline antibiotics bacteria residue.It is high the invention solves existing tetracycline antibiotics bacteria residue processing cost, the problems such as remaining environmental risk after processing.The present invention is using persulfate as oxidant, ferrous sulfate as activator, and the residual quantity to tetracycline antibiotics is 1000~2500mg/kg, and the tetracycline antibiotics bacteria residue of pH=2.0~4.5 is handled.The present invention is up to 99.5% using ferrous ion activation persulfate to tetracycline antibiotics removal efficiency, and sterilizing ability is strong, and process cycle is short, can be completed no more than 1 hour.
Description
Technical field
The present invention relates to the harmless treatment of tetracycline antibiotics bacteria residue and resource utilization method.
Background technology
China is antibiotics production big country, and China's antibiotic yield in 2011 is 111.6 ten thousand tons and accounts for world market total amount
More than 70%.The annual production of wherein tetracycline antibiotics terramycin accounts for the 90% of global yield.Produced according to every production 1t antibiotic
Raw 8-10t wet bacteria slags estimation, China every year the caused terramycin strain quantity of slag more than 150,000 tons.Macrometabolic element is rich in bacteria residue
Matter, but because wherein containing a small amount of antibiotic residue, to prevent antibiotic residue from triggering the risk of bacterial resistance in environment, antibiotic
Bacteria residue must first pass around processing and remove wherein antibiotic residue, then can just be used.If mishandling, can seriously endanger
Evil ecological environment and health.Antibiotic bacterium dregs have been put into new revision within 2008《National Hazard waste register》, antibiosis
The culture medium waste that plain bacteria residue belongs to during chemicals production of raw medicine, must be managed by hazardous waste.Therefore how
Rationally disposal antibiotic bacterium dregs, the outlet for solving antibiotic bacterium dregs have become very urgent task.
Typical tetracycline antibiotics mainly includes terramycin, tetracycline, aureomycin and fortimicin, and its bacteria residue is mainly by bacterium
Filament, remaining culture medium, fermentating metabolism product composition, wherein containing substantial amounts of polysaccharide, protein and several amino acids and micro
Element, simultaneously containing a small amount of antibiotic residue.And domestic pharmaceutical factory is substantially carried out burning disposal to this kind of antibiotic bacterium dregs at present,
But because bacteria residue water content is larger (about more than 75%), not only burning cost is too high, can bring new atmosphere pollution risk, and
Cause resource serious waste.At present, the problem has had influence on the sound development of China's pharmaceutical industry.Therefore, one kind is found such as
What is the need remained except the life of bacteria residue moderate resistance is plain, nutriment contained by rational exploitation and utilization bacteria residue, realize the innoxious and recycling of bacteria residue,
This is to economizing on resources, preventing the pollution of the environment, developing a circular economy has great importance.
For the realistic problem such as antibiotic bacterium dregs yield is big, intractability is big,《Pharmaceuticals industry pollution prevention technique political affairs
Plan》" reutilization technology of encouraging exploitation fermentation bacteria residue in production technology, harmless treatment skill are proposed in (exposure draft)
Art, comprehensive utilization technique " policy and suggestion.
It is main to close in the method that the relevant tetracycline antibiotics bacteria residue processing delivered both at home and abroad at present utilizes with Fertilizer Transformed
Note the wherein removal of antibiotic residue and the fertilizer efficiency as organic fertilizer, not yet concern handle after bacteria residue and made fertilizer whether
Containing tetracycline antibiotics drug-fast bacteria, whether there is security as Fertilizer application.
The content of the invention
It is high the invention solves existing tetracycline antibiotics bacteria residue processing cost, environmental risk etc. is remained after processing and is asked
A kind of topic, there is provided method that organic fertilizer is produced using tetracycline antibiotics bacteria residue.Tetracycline antibiotics of the present invention includes soil
Mycin, tetracycline, aureomycin and fortimicin.
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of the present invention, it is to follow the steps below
's：
First, Fresh antibiotic bacteria residue is gathered, it is 80~90% to add water to adjust to moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 5.5-6.5；
The 3rd, persulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the tetracycline antibiotics in bacteria residue and the mol ratio of over cure acid group and iron are 1：60~80：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, 0.3~1.0h of oxidation processes；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue precipitation is mixed into drying with auxiliary material humic acid or bentonite and is granulated, that is, completes described utilization four
Ring class antibiotic bacterium dregs produce organic fertilizer；
The residual quantity of tetracycline antibiotics is 1000~2500mg/kg in described antibiotic bacterium dregs, pH=2.0~4.5.
Described persulfate is potassium peroxydisulfate or ammonium persulfate.
The present invention principle be：In a heated condition, persulfate is activated by ferrous ion, improves potentiometric titrations
Yield, potentiometric titrations have very strong oxidisability, can effectively destroy tetracycline antibiotics molecular structure, while kill bacteria residue
In antibiotic resistant bacteria, bacteria residue organic fertilizer is used without antibiotic resistant bacteria and bacterial resistance is not triggered in soil
Security improves, so as to realize the harmless treatment of bacteria residue and recycling.
The removal that tetracycline antibiotics remains in the high solid phase bacteria residue slurry of the present invention is different from organic matter removal in waste water, gives up
The target of water process is the organic matter of all kinds in water removal, and the target of bacteria residue processing is to remove antibiotic residue and retain
The organic nutrient substance beneficial to plant growth such as polysaccharide, protein, amino acid, i.e., organic matter is selective removal in bacteria residue,
And ferrous ion activation improves the clearance of tetracycline antibiotics residual, while have the function that to kill drug-fast bacteria in bacteria residue.
Compared with antibiotic bacterium Slag treatment, ferrous ion activation persulfate is used for organic matter removal in waste water, may
If water reuse is difficult to the problems such as up to standard after bringing the secondary pollution and processing of iron ion and sulfate；And it is used for antibiotic
Bacteria residue processing is then different, and persulfate (potassium peroxydisulfate or ammonium persulfate) can be transformed into potassium sulfate or sulfuric acid in use
Ammonium, potassium and nitrogen are soil needed nutrient matter, and sulfate radical is in the fully acceptable scope of soil, and micro iron rule is crop life
Long required trace element.
The present invention includes following beneficial effect：
1. fertilizer reparation technology is simple in the present invention, easily operated, processing cost is low.
2. tetracycline antibiotics degradation efficiency is high in the present invention, tetracycline antibiotics drug-fast bacteria can be killed effectively in bacteria residue
Go out, fertilizer it is safe to use.
3. the oxidant used in the present invention is potassium peroxydisulfate or ammonium persulfate, they change during bacteria residue is handled
Into potassium sulfate or ammonium sulfate, be advantageous to improve the content for producing the nutritional ingredient of potassium and nitrogen in fertilizer.
4. the teracycline antibiotic residues amount that the present invention is handled is 1000~3500mg/kg, content is very high, and bacterium
There are other complicated ingredients in slag, the use to oxidant causes very big difficulty, how to handle the Fourth Ring class of such high concentration
Antibiotic bacterium dregs, it is currently that no correlation technique can be used for reference.The present invention activates persulfate to Fourth Ring using ferrous ion
Plain class antibiotic removal efficiency is up to 99.5%, and sterilizing ability is strong, and process cycle is short, can be completed no more than 1 hour.
5. activator ferrous ion used is finally transformed into plant growth needs in use in the present invention
Trace element, iron are the prothetic groups of many enzymes (such as cytochromes, cytochrome oxidase and catalase), are metabolized at it
Played an important role in the electron transmission of journey.Material necessary to iron is also Chlorophyll synthesis, being catalyzed in the enzyme of Chlorophyll synthesis has
The activity expression of two or three of enzymes needs Fe2+。
The addition of ferrous ions of the present invention makes the content of trace elements iron in fertilizer improve about 0.07%~0.25%, has
After machine fertilizer is manured into soil by the dose less than 1%, the content of iron at most 7~25 milligrams of increase in per kilogram soil, completely not
Soil environment quality can be influenceed, and plays the effect of its trace nutrient.
6. treatment process condition is relatively mild in the present invention, low for the organic matter nutritional ingredient destructiveness in bacteria residue,
It is advantageously implemented the recovery of nutriment.
7. the present invention can provide a kind of method of bacteria residue safe disposal and recycling for pharmacy corporation, at reduction
Cost is managed, certain economic benefit is brought for enterprise.
Embodiment
Embodiment one：A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of present embodiment,
It is followed the steps below：
First, Fresh antibiotic bacteria residue is gathered, it is 80~90% to add water to adjust to moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 5.5-6.5；
The 3rd, persulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the tetracycline antibiotics in bacteria residue and the mol ratio of over cure acid group and iron are 1：60~80：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, 0.3~1.0h of oxidation processes；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue precipitation is mixed into drying with auxiliary material humic acid or bentonite and is granulated, that is, completes described utilization four
Ring class antibiotic bacterium dregs produce organic fertilizer；
The residual quantity of tetracycline antibiotics is 1000~2500mg/kg in antibiotic bacterium dregs, pH=2.0~4.5.
Tetracycline antibiotics bacteria residue described in present embodiment is terramycin bacteria residue, tetracycline bacterial dreg, aureomycin bacteria residue or
Fortimicin bacteria residue.
Embodiment two：Present embodiment is unlike embodiment one：Fourth Ring class antibiosis in bacteria residue
Element is 1 with the mol ratio of over cure acid group and iron：65~80：1.It is other identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one：Fourth Ring class antibiosis in bacteria residue
Element is 1 with the mol ratio of over cure acid group and iron：70~80：1.It is other identical with embodiment one.
Embodiment four：Present embodiment is unlike embodiment one：Fourth Ring class antibiosis in bacteria residue
Element is 1 with the mol ratio of over cure acid group and iron：70~75：1.It is other identical with embodiment one.
Embodiment five：Present embodiment is unlike embodiment one：Fourth Ring class antibiosis in bacteria residue
Element is 1 with the mol ratio of over cure acid group and iron：73：1.It is other identical with embodiment one.
Embodiment six：Present embodiment is unlike embodiment one：Fourth Ring class in antibiotic bacterium dregs
The residual quantity of antibiotic is 1000~1500mg/kg, pH=2.0~4.5.It is other identical with embodiment one.
Embodiment seven：Present embodiment is unlike embodiment one：Fourth Ring class in antibiotic bacterium dregs
The residual quantity of antibiotic is 1500~2500mg/kg, pH=2.0~4.5.It is other identical with embodiment one.
Embodiment eight：Present embodiment is unlike embodiment one：Fourth Ring class in antibiotic bacterium dregs
The residual quantity of antibiotic is 2000~2500mg/kg, pH=2.0~4.5.It is other identical with embodiment one.
Embodiment nine：Present embodiment is unlike embodiment one：Fourth Ring class in antibiotic bacterium dregs
The residual quantity of antibiotic is 2200mg/kg, pH=2.0~4.5.It is other identical with embodiment one.
Embodiment ten：Present embodiment is unlike embodiment one：The bacterium that will be handled through step 3
Slag is placed in 65~95 DEG C of water-baths, 0.5~1.0h of oxidation processes.It is other identical with embodiment one.
Present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several embodiments
Contract sample can also realize the purpose of invention.
Beneficial effects of the present invention are verified by following examples：
Embodiment 1
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of the present invention, it is to follow the steps below
's：
First, fresh terramycin bacteria residue is gathered, it is 80% to add water regulation moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 6.0；
The 3rd, potassium peroxydisulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the terramycin in bacteria residue and the mol ratio of over cure acid group and iron are 1：80：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, oxidation processes 1h；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue is precipitated and mixes drying granulation with auxiliary material humic acid or bentonite, i.e., what completion was described utilizes soil
Mycin bacteria residue produces organic fertilizer；
The residual quantity of terramycin is 2000mg/kg, pH=2.8 in antibiotic bacterium dregs.
The present embodiment is up to 99.5% using ferrous ion activation potassium peroxydisulfate to terramycin removal efficiency, sterilizing ability
By force, process cycle is short, can be completed no more than 1 hour.
Terramycin drug-fast bacteria drug resistant gene in the soil of bacteria residue organic fertilizer and application fertilizer (dose 1%) after 1~30 day
Testing result be negative.
Embodiment 2
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of the present invention, it is to follow the steps below
's：
First, fresh aureomycin bacteria residue is gathered, it is 85% to add water regulation moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 6.3；
The 3rd, potassium peroxydisulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the aureomycin in bacteria residue and the mol ratio of over cure acid group and iron are 1：65：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, oxidation processes 1h；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue is precipitated and mixes drying granulation with auxiliary material humic acid or bentonite, i.e., what completion was described utilizes gold
Mycin bacteria residue produces organic fertilizer；
The residual quantity of aureomycin is 1300mg/kg, pH=3.0 in antibiotic bacterium dregs.
The present embodiment is up to 99.5% using ferrous ion activation potassium peroxydisulfate to aureomycin removal efficiency, sterilizing ability
By force, process cycle is short, can be completed no more than 1 hour.
Aureomycin drug-fast bacteria drug resistant gene in the soil of bacteria residue organic fertilizer and application fertilizer (dose 1%) after 1~30 day
Testing result be negative.
Embodiment 3
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of the present invention, it is to follow the steps below
's：
First, fresh tetracycline bacterial dreg is gathered, it is 90% to add water regulation moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 6.2；
The 3rd, potassium peroxydisulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the tetracycline in bacteria residue and the mol ratio of over cure acid group and iron are 1：72：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, oxidation processes 1h；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue precipitation is mixed into drying with auxiliary material humic acid or bentonite and is granulated, that is, completes described utilization four
Ring element bacteria residue produces organic fertilizer；
The residual quantity of tetracycline is 1800mg/kg, pH=3.5 in antibiotic bacterium dregs.
The present embodiment is up to 99.5% using ferrous ion activation potassium peroxydisulfate to tetracycline removal efficiency, sterilizing ability
By force, process cycle is short, can be completed no more than 1 hour.
Tetracycline resistant bacterium drug resistant gene in the soil of bacteria residue organic fertilizer and application fertilizer (dose 1%) after 1~30 day
Testing result be negative.
Embodiment 4
A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue of the present invention, it is to follow the steps below
's：
First, fresh tetracycline bacterial dreg is gathered, it is 90% to add water regulation moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 6.2；
The 3rd, ammonium persulfate is separately added into the bacteria residue handled through step 2 as oxidant, ferrous sulfate as activator
In, mix；Wherein, the tetracycline in bacteria residue and the mol ratio of over cure acid group and iron are 1：72：1；
4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, oxidation processes 1h；
5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifugation
20min, obtained bacteria residue precipitation is mixed into drying with auxiliary material humic acid or bentonite and is granulated, that is, completes described utilization four
Ring element bacteria residue produces organic fertilizer；
The residual quantity of tetracycline is 1800mg/kg, pH=3.5 in antibiotic bacterium dregs.
The present embodiment is up to 99.5% using ferrous ion activation ammonium persulfate to tetracycline removal efficiency, sterilizing ability
By force, process cycle is short, can be completed no more than 1 hour.
Tetracycline resistant bacterium drug resistant gene in the soil of bacteria residue organic fertilizer and application fertilizer (dose 1%) after 1~30 day
Testing result be negative.
Claims (10)
- A kind of 1. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue, it is characterised in that it is to follow the steps below 's：First, Fresh antibiotic bacteria residue is gathered, it is 80~90% to add water to adjust to moisture content, obtains pending bacteria residue；2nd, the NaOH solution for being 5M with concentration adjusts pending bacteria residue pH to 5.5-6.5；3rd, it is separately added into the bacteria residue handled through step 2, mixes as activator using persulfate as oxidant, ferrous sulfate It is even；Wherein, the tetracycline antibiotics in bacteria residue and the mol ratio of over cure acid group and iron are 1：60~80：1；4th, the bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, 0.3~1.0h of oxidation processes；5th, the bacteria residue after the completion of reacting is cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, centrifuges 20min, Obtained bacteria residue is precipitated and mixes drying granulation with auxiliary material humic acid or bentonite, i.e., completion is described is resisted using Fourth Ring class Raw plain bacteria residue produces organic fertilizer；The residual quantity of tetracycline antibiotics is 1000~2500mg/kg in antibiotic bacterium dregs, pH=2.0~4.5.
- A kind of 2. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 1, it is characterised in that Tetracycline antibiotics and the mol ratio of over cure acid group and iron in bacteria residue are 1：65~80：1.
- A kind of 3. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 2, it is characterised in that Tetracycline antibiotics and the mol ratio of over cure acid group and iron in bacteria residue are 1：70~80：1.
- A kind of 4. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 3, it is characterised in that Tetracycline antibiotics and the mol ratio of over cure acid group and iron in bacteria residue are 1：70~75：1.
- A kind of 5. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 4, it is characterised in that Described persulfate is potassium peroxydisulfate or ammonium persulfate.
- A kind of 6. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 1, it is characterised in that The residual quantity of tetracycline antibiotics is 1000~1500mg/kg in antibiotic bacterium dregs, pH=2.0~4.5.
- A kind of 7. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 6, it is characterised in that The residual quantity of tetracycline antibiotics is 1500~2500mg/kg in antibiotic bacterium dregs, pH=2.0~4.5.
- A kind of 8. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 7, it is characterised in that The residual quantity of tetracycline antibiotics is 2000~2500mg/kg in antibiotic bacterium dregs, pH=2.0~4.5.
- A kind of 9. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 8, it is characterised in that Described tetracycline antibiotics bacteria residue is terramycin bacteria residue, tetracycline bacterial dreg, aureomycin bacteria residue or fortimicin bacteria residue.
- A kind of 10. method that organic fertilizer is produced using tetracycline antibiotics bacteria residue according to claim 1, it is characterised in that The bacteria residue handled through step 3 is placed in 65~95 DEG C of water-baths, 0.5~1.0h of oxidation processes.
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| CN112934932A (en) * | 2021-04-14 | 2021-06-11 | 同济大学 | Harmless treatment method for antibiotic mushroom dregs |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108188165A (en) * | 2017-12-22 | 2018-06-22 | 上海市农业科学院 | The method of chloromycetin series antibiotics in a kind of degrade soil or clay |
| CN108188165B (en) * | 2017-12-22 | 2020-05-26 | 上海市农业科学院 | Method for degrading chloramphenicol antibiotics in soil or clay |
| CN108726829A (en) * | 2018-06-19 | 2018-11-02 | 中国农业大学 | A kind of method of situ catalytic persulfate abatement livestock and poultry feces antibiotic |
| CN108726829B (en) * | 2018-06-19 | 2020-09-01 | 中国农业大学 | Method for reducing livestock and poultry manure antibiotic by in-situ catalysis of persulfate |
| CN108977468A (en) * | 2018-09-06 | 2018-12-11 | 河北省科学院生物研究所 | A method of improving antibiotic bacterium dregs anaerobic fermentation efficiency and stability |
| CN112409033A (en) * | 2020-11-29 | 2021-02-26 | 上海化工研究院有限公司 | Method for preparing fertilizer product by recycling tetracyclic antibiotic fermentation waste residues |
| CN112934932A (en) * | 2021-04-14 | 2021-06-11 | 同济大学 | Harmless treatment method for antibiotic mushroom dregs |
| 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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Application publication date: 20171117 |