CN107311729A - A kind of method that utilization lincomycin fungi residues produce organic fertilizer - Google Patents
A kind of method that utilization lincomycin fungi residues produce organic fertilizer Download PDFInfo
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- CN107311729A CN107311729A CN201710660614.6A CN201710660614A CN107311729A CN 107311729 A CN107311729 A CN 107311729A CN 201710660614 A CN201710660614 A CN 201710660614A CN 107311729 A CN107311729 A CN 107311729A
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- lincomycin
- fungi residues
- organic fertilizer
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- lincomycin fungi
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- 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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
- C05F5/006—Waste from chemical processing of material, e.g. diestillation, roasting, cooking
- C05F5/008—Waste from biochemical processing of material, e.g. fermentation, breweries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Abstract
A kind of method that utilization lincomycin fungi residues produce organic fertilizer, it is related to the harmless treatment and recovery of lincomycin fungi residues.The method of the present invention, to realize harmless treatment and the recycling of lincomycin fungi residues.Specially：Gather after fresh lincomycin fungi residues, regulation moisture content and pH value, plus after potassium peroxydisulfate and zinc acetate processing, precipitation is collected by centrifugation, organic fertilizer is made.Lincomycin residual is destroyed in the present invention, remove, and contained antibiotic resistant bacteria is inactivated in bacteria residue.This method process is simple, it is easy to operate.The present invention is high to lincomycin removal efficiency using potassium peroxydisulfate, and up to 99.9%, processing cost is low, the cycle is short, and half an hour can complete.Bacteria residue organic fertilizer is without antibiotic resistant bacteria and does not trigger bacterial resistance in soil, safe to use.
Description
Technical field
The present invention relates to the harmless treatment of lincomycin fungi residues and recycling.
Background technology
China is the production of antibiotic, using, big export country, and its bacteria residue is every in process of production for China's ferment antibiotics
About 2,000,000 tons of the discharge capacity in year, is rich in a large number of nutrients, but be anti-because wherein containing a small amount of antibiotic residue in bacteria residue
Only antibiotic residue triggers the risk of bacterial resistance in environment, and antibiotic bacterium dregs must first pass around processing and remove wherein antibiotic
Residual, then can just be used.But up to the present, China's antibiotic bacterium dregs still lack safely and effectively innoxious and resource
Change processing method, the overwhelming majority can only burning disposal, not only cause ample resources to waste, and burning disposal cost is high, exists
The risk of secondary pollution.Meanwhile, the high cost of bacteria residue processing is severely impacted the sound development of pharmaceutical industry.
Lincomycin is wide variety of anti-microbial type antibiotic in the world, and 80% lincomycin bulk drug originates in China,
It is main to be made by microbe fermentation method.Microbe fermentation method produces substantial amounts of accessory substance-lincomycin when producing lincomycin
Bacteria residue, it mainly includes fermentation mycelium, complete lincomycin, a small amount of inorganic nutritive element is not extracted and is not utilized largely
Complete culture substrate.Main organic matter is protein and polysaccharide in bacteria residue, and 15% and 38% that wet basis content is accounted for respectively is left
The right side, with huge application value, animal feed raw material is used as before 2002.Remaining woods in lincomycin fungi residues can be mould
The concentration of element is significantly larger than content of lincomycin in water environment and soil environment for 1200-1500mg/kg, improper due to bacteria residue
Disposal wherein lincomycin easily enters soil and groundwater, and migrates wherein, aggravate the generation of drug-resistant microorganism with
The propagation of drug resistant gene, influence animal and plant growth and microecological balance, and human health is influenceed indirectly.China will be anti-in 2008
Raw element bacteria residue is included in danger wastes register, and its current unique disposal options are to burn, and burning not only causes the wasting of resources to return
Pharmacy corporation brings huge financial burden.Therefore it is badly in need of a kind of safe and effective processing method of exploitation, to remove lincomycin
Bacteria residue in remain lincomycin, to realize the harmlessness disposing of bacteria residue and the recycling of next step.
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.
Lincomycin belongs to lincosamides, and heat endurance is good, can be stabilized 1 month at 70 DEG C.Current state
It is inside and outside to have for lincomycin a small amount of in environment using ozone oxidation, the report of optically catalytic TiO 2 oxidation removal, but
Content of lincomycin is remained in lincomycin fungi residues higher, and matrix is complicated, the application of conventional method is restricted.It is domestic at present
The outer research for removing residual lincomycin in lincomycin fungi residues is less, in the research for being concentrated mainly on bioanalysis removal.
The A of patent No. CN 102676407 Chinese patent discloses one kind can using residual woods in saccharomycete degraded lincomycin fungi residues
The method of mycin；It is the Yeast Growth breeding being screened for as solid medium using lincomycin fungi residues, and then it is residual to degrade
The lincomycin stayed.Inoculating strain is low for the selectivity of lincomycin in the method, and removal efficiency is low, only removes within 14 days
33.80% lincomycin；And during this, degradation bacteria strains can produce resistance to lincomycin, contain degradation bacteria after processing
The further recycling of lincomycin fungi residues of strain is restricted.The A of patent No. CN 105502775 Chinese patent is disclosed
A kind of method of antibiotic in persulfate degradation water, the wherein antibiotic concentration scope of application is 20-200mg/L, and only fitted
It is mould for penicillin, Amoxicillin, Ciprofloxacin, Ofloxacin, ROX, CLA, Amikacin, two property
One or more of mixtures in element, sulphadiazine, Tetracyclines and chloromycetin；High solid phase of how degrading is not provided
In antibiotic, particularly with antibiotic bacterium dregs, containing Various Complex composition, and antibiotic concentration is high, and the patent is not applied to simultaneously.
Lincomycin molecular structure is different from above-mentioned antibiotic, with lincomycin clearance in PROCESS FOR TREATMENT bacteria residue described in this patent only
For 58%.
In view of China there is no lincomycin fungi residues safely and effectively processing method at present, therefore, being badly in need of one kind can be handled
The technology of antibiotic bacterium dregs, to realize harmless treatment and the safe utilization of antibiotic bacterium dregs.
The content of the invention
It is an object of the invention to provide a kind of method that utilization lincomycin fungi residues produce organic fertilizer, to realize that woods can
The harmless treatment of mycin bacteria residue and recycling.
The method that a kind of utilization lincomycin fungi residues of the present invention produce organic fertilizer, is carried out according to the following steps：
First, fresh lincomycin fungi residues are gathered, it is 85~90% to add deionized water regulation moisture content, obtains pending bacterium
Slag；
2nd, the NaOH solution for being 5M with concentration adjusts pending rear bacteria residue pH to 7~8；
3rd, potassium peroxydisulfate and zinc acetate are added separately in the lincomycin fungi residues after step 2 regulation pH, mixed；Its
In, the mol ratio of lincomycin and over cure acid group and zinc is 1：22~26：0.8；
4th, the bacteria residue handled through step 3 is placed in 80 DEG C of water-baths, 0.3~1.0h of oxidation processes；
5th, the lincomycin fungi residues after the completion of reacting are cooled to room temperature, in the condition that rotating speed is 4000~8000r/min
Under, 20min is centrifuged, by the precipitation drying granulation of obtained bacteria residue, organic fertilizer is made, that is, completes described utilization lincomycin fungi residues
Produce organic fertilizer；The lincomycin residual quantity of described lincomycin fungi residues is 1200~1500mg/kg, pH=4~5.
The present invention principle be：In a heated condition, potassium peroxydisulfate (K is activated using zinc ion2S2O8) to promote sulfate radical
Free radical is produced, and potentiometric titrations have very strong oxidisability, can destroy lincomycin molecular structure in bacteria residue, and kill bacteria residue
In antibiotic resistant bacteria, make bacteria residue organic fertilizer without antibiotic resistant bacteria and bacterial resistance is not triggered in soil, use
Security is improved, so as to realize harmless treatment and the recycling of bacteria residue.
The removal that lincomycin is remained in the high solid phase bacteria residue slurry of the present invention is different from organic matter removal in waste water, at waste water
The target of reason is the organic matter of all kinds in water removal, and the target of bacteria residue processing is to remove antibiotic residue and retain many
The organic nutrient substance beneficial to plant growth such as sugar, protein, amino acid, i.e., organic matter is selective removal in bacteria residue, and
Zinc ion activation is conducive to the removal that lincomycin is remained.
Moreover, the moisture content of lincomycin fungi residues and be by strict with potassium peroxydisulfate and zinc acetate mol ratio in the present invention
Condition limitation, above-mentioned condition of the invention is set based on the situation of lincomycin high concentration in bacteria residue, not arbitrarily
Change, it is entirely different operation technique with Antibiotics of Low Concentration in processing water；The potassium peroxydisulfate and zinc acetate mistake of the application
Many additions, the removal efficiency of antibiotic will not be significantly improved, but cause the reduction of nutrition organic matter in bacteria residue, unfavorable
Produced in organic fertilizer；Cross and do not have obvious removal effect at least；Therefore, bacteria residue processing is only carried out in the conditions of the invention
It can be only achieved 99.9% removal effect.
Compared with antibiotic bacterium Slag treatment, zinc ion activation persulfate is used for organic matter removal in waste water, may
Bring the secondary pollution problem of zinc ion and sulfate；And it is used for that antibiotic bacterium Slag treatment is then different, potassium peroxydisulfate was being used
Cheng Zhonghui is transformed into potassium sulfate, and potassium is soil needed nutrient matter, and sulfate radical is and micro in the fully acceptable scope of soil
Zinc is then the trace element needed for plant growth.
Advantages of the present invention：
1. lincomycin is efficiently destroyed, removed in the present invention, drug-fast bacteria is inactivated in bacteria residue, and technique is simple, it is easy to
Operation, organic fertilizer is safe to use.
2. the oxidant used in the present invention is potassium peroxydisulfate (K2S2O8) potassium sulfate (K that generates after processing2SO4) can be used for
Follow-up potash fertilizer raw material.
3. the lincomycin residual quantity that the present invention is handled is 1200~1500mg/kg, content is very high, and in bacteria residue also
There are other complicated ingredients, the use to oxidant causes very big difficulty, how to handle the lincomycin fungi residues of such high concentration,
It is currently that no correlation technique can be used for reference.Potassium peroxydisulfate is activated to lincomycin removal efficiency using zinc ion in the present invention
Up to 99.9%, while sterilizing ability is strong, process cycle is short, and half an hour can complete.
4. treatment conditions are relatively mild in the present invention, low for the organic destruction degree in bacteria residue, battalion is advantageously implemented
Support the recovery of material.
5. the present invention can provide a kind of method of bacteria residue safe disposal and recycling for pharmacy corporation, reduction is processed into
This while, brings potential economic benefit.
6. activator zinc acetate used is transformed into organic battalion of plant growth needs in use in the present invention
Material and trace element are supported, zinc can promote crop photosynthesis, promote auxin to be formed.The use of activator zinc acetate, makes fertilizer
The content of trace element zinc improves about 0.06%, after organic fertilizer is manured into soil by the dose less than 1%, per kilogram soil in material
About 6 milligrams of the content increase of middle zinc, does not interfere with primary standard Zn content in national standard of soil environment quality and is less than 100mg/
Kg requirement, but play the effect of its trace nutrient.
Brief description of the drawings
Fig. 1 is the removal figure for remaining lincomycin in embodiment one in lincomycin fungi residues processing procedure.
Embodiment
Embodiment one：The method that a kind of utilization lincomycin fungi residues of present embodiment produce organic fertilizer, by with
Lower step is carried out：
First, fresh lincomycin fungi residues are gathered, it is 85~90% to add deionized water regulation moisture content, obtains pending bacterium
Slag；
2nd, the NaOH solution for being 5M with concentration adjusts pending rear bacteria residue pH to 7~8；
3rd, potassium peroxydisulfate and zinc acetate are added separately in the lincomycin fungi residues after step 2 regulation pH, mixed；Its
In, the mol ratio of lincomycin and over cure acid group and zinc is 1：22~26：0.8；
4th, the bacteria residue handled through step 3 is placed in 80 DEG C of water-baths, 0.3~1.0h of oxidation processes；
5th, the lincomycin fungi residues after the completion of reacting are cooled to room temperature, in the condition that rotating speed is 4000~8000r/min
Under, 20min is centrifuged, by the precipitation drying granulation of obtained bacteria residue, organic fertilizer is made, that is, completes described utilization lincomycin fungi residues
Produce organic fertilizer；The lincomycin residual quantity of described lincomycin fungi residues is 1200~1500mg/kg, pH=4~5.
Embodiment two：Present embodiment from unlike embodiment one：Gather fresh lincomycin fungi
Slag, it is 85~90% to add deionized water regulation moisture content, obtains pending bacteria residue.It is other identical with embodiment one.
Embodiment three：Present embodiment from unlike embodiment one：PH to 7.5 in step 2.
It is other identical with embodiment one.
Embodiment four：Present embodiment from unlike embodiment one：Lincomycin and potassium peroxydisulfate
And the mol ratio of zinc is 1：24~26：0.8.It is other identical with embodiment one.
Embodiment five：Present embodiment from unlike embodiment one：Lincomycin and potassium peroxydisulfate
And the mol ratio of zinc is 1：25：0.8.It is other identical with embodiment one.
Embodiment six：Present embodiment from unlike embodiment one：Lincomycin and over cure acid group
And the mol ratio of zinc is 1：26：0.8.It is other identical with embodiment one.
Embodiment seven：Present embodiment from unlike embodiment one：Lincomycin and over cure acid group
And the mol ratio of zinc is 1：22：0.8.It is other identical with embodiment one.
Embodiment eight：Present embodiment from unlike embodiment one：Lincomycin and potassium peroxydisulfate
And the mol ratio of zinc acetate is 1：23：0.8.It is other identical with embodiment one.
Embodiment nine：Present embodiment from unlike embodiment one：Lincomycin and over cure acid group
And the mol ratio of zinc is 1：24：0.8.It is other identical with embodiment one.
Embodiment ten：Present embodiment from unlike embodiment one：Oxidation processes in step 4
0.5h.It is other identical with embodiment one.
Embodiment 11：Present embodiment from unlike embodiment one：Described lincomycin fungi
The lincomycin residual quantity of slag is 1200~1500mg/kg, pH=4.1~4.5.It is other identical with embodiment one.
Embodiment 12：Present embodiment from unlike embodiment one：Described lincomycin fungi
The lincomycin residual quantity of slag is 1200~1500mg/kg, pH=4.16.It is other identical with embodiment one.
Embodiment 13：Present embodiment from unlike embodiment one：Described lincomycin fungi
The lincomycin residual quantity of slag is 1200~1300mg/kg, pH=4.16.It is other identical with embodiment one.
Embodiment 14：Present embodiment from unlike embodiment one：Described lincomycin fungi
The lincomycin residual quantity of slag is 1200~1400mg/kg, pH=4.16.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 effect of the present invention is verified using following examples and contrast test：
Embodiment 1
A kind of method for producing organic fertilizer using lincomycin fungi residues of the present embodiment is carried out according to the following steps：
1. the fresh lincomycin fungi residues of 1kg (lincomycin residual quantity is 1200-1500mg/kg, pH=4.16) are gathered, plus
Enter deionized water regulation moisture content to be 70% and adjust pH to 7.28 with 5M NaOH；Potassium peroxydisulfate is separately added into after being mixed
And zinc acetate, the mol ratio of lincomycin and over cure acid group and zinc is 1：24~26：0.8, mix uniformly stirred after 80 DEG C again
Mix processing 0.5h.
2. the bacteria residue obtained through step 1 is under conditions of rotating speed 4000-8000r/min, 20min is centrifuged, is precipitated, and
Progress drying granulation in slurry-spraying pelletizing machine is added to, organic fertilizer product is made, the harmless treatment of bacteria residue is completed.
Bacteria residue moisture content used is 70% in the present embodiment, the pH=7.28 of bacteria residue after processing, and lincomycin clearance is
98%, bacteria residue organic fertilizer and apply lincomycin drug-fast bacteria drug resistant gene in fertilizer (dose 1%) soil after 1~30 day
Testing result is negative.Bacteria residue centrifugation gained precipitation is added to progress drying granulation in slurry-spraying pelletizing machine, organic fertilizer production is made
Product, complete the harmless treatment of bacteria residue.
Embodiment 2
A kind of method for producing organic fertilizer using lincomycin fungi residues of the present embodiment is carried out according to the following steps：
1. the fresh lincomycin fungi residues of 1kg (lincomycin residual quantity is 1300~1500mg/kg, pH=4.16) are gathered,
Deionized water regulation moisture content is added to be 85% and adjust pH to 7.50 with 5M NaOH；Persulfuric acid is separately added into after being mixed
Potassium and zinc acetate, lincomycin are 1 with the mol ratio for crossing over cure acid group and zinc：22~24：0.8, mix again after 80 DEG C of water
0.5h is handled in bath.
2. the bacteria residue obtained through step 1 is under conditions of rotating speed 4000-8000r/min, 20min is centrifuged, is precipitated, and
Progress drying granulation in slurry-spraying pelletizing machine is added to, organic fertilizer product is made, the harmless treatment of bacteria residue is completed.
Bacteria residue moisture content used is 85% in the present embodiment, the pH=7.5 of bacteria residue after processing, and lincomycin clearance is
99%, bacteria residue organic fertilizer and apply lincomycin drug-fast bacteria drug resistant gene in fertilizer (dose 1%) soil after 1~30 day
Testing result is negative.Bacteria residue centrifugation gained precipitation is added to progress drying granulation in slurry-spraying pelletizing machine, organic fertilizer production is made
Product, complete the harmless treatment of bacteria residue.
Embodiment 3
A kind of method for producing organic fertilizer using lincomycin fungi residues of the present embodiment is carried out according to the following steps：
1. the fresh lincomycin fungi residues of 1kg (lincomycin residual quantity is 1200~1500mg/kg, pH=4.16) are gathered,
Deionized water regulation moisture content is added to be 80% and adjust pH to 7.28 with 5M NaOH；Persulfuric acid is separately added into after being mixed
The mol ratio of potassium and zinc acetate, lincomycin and over cure acid group and zinc is 1：25：0.8, mix again after place in 80 DEG C of water-baths
Manage 0.5h.
2. the bacteria residue obtained through step 1 is under conditions of rotating speed 4000-8000r/min, 20min is centrifuged, is precipitated, and
Progress drying granulation in slurry-spraying pelletizing machine is added to, organic fertilizer product is made, the harmless treatment of bacteria residue is completed.
Bacteria residue moisture content used is 80% in the present embodiment, the pH=7.28 of bacteria residue after processing, and lincomycin clearance is
99.9%, bacteria residue organic fertilizer and apply lincomycin drug-fast bacteria drug resistant gene in fertilizer (dose 1%) soil after 1~30 day
Testing result be negative.Bacteria residue centrifugation gained precipitation is added to progress drying granulation in slurry-spraying pelletizing machine, organic fertilizer is made
Product, completes the harmless treatment of bacteria residue.
Claims (10)
1. a kind of method that utilization lincomycin fungi residues produce organic fertilizer, it is characterised in that it is followed the steps below：
First, fresh lincomycin fungi residues are gathered, it is 85~90% to add deionized water regulation moisture content, obtains pending bacteria residue；
2nd, the NaOH solution for being 5M with concentration adjusts pending rear bacteria residue pH to 7~8；
3rd, potassium peroxydisulfate and zinc acetate are added separately in the lincomycin fungi residues after step 2 regulation pH, mixed；Wherein,
The mol ratio of lincomycin and over cure acid group and zinc is 1：22~26：0.8；
4th, the bacteria residue handled through step 3 is placed in 80 DEG C of water-baths, 0.3~1.0h of oxidation processes；
5th, the lincomycin fungi residues after the completion of reacting are cooled to room temperature, under conditions of rotating speed is 4000~8000r/min, from
Heart 20min, by the precipitation drying granulation of obtained bacteria residue, makes organic fertilizer, that is, completes described utilization lincomycin fungi residues and produce
Organic fertilizer；The lincomycin residual quantity of described lincomycin fungi residues is 1200~1500mg/kg, pH=4~5.
2. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that collection
Fresh lincomycin fungi residues, it is 85~90% to add deionized water regulation moisture content, obtains pending bacteria residue.
3. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that step
PH to 7.5 in two.
4. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that Lin Ke
The mol ratio of mycin and over cure acid group and zinc is 1：24~26：0.8.
5. the method that a kind of utilization lincomycin fungi residues according to claim 4 produce organic fertilizer, it is characterised in that Lin Ke
The mol ratio of mycin and over cure acid group and zinc is 1：25：0.8.
6. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that step
Oxidation processes 0.5h in four.
7. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that described
Lincomycin fungi residues lincomycin residual quantity be 1200~1500mg/kg, pH=4.1~4.5.
8. the method that a kind of utilization lincomycin fungi residues according to claim 7 produce organic fertilizer, it is characterised in that described
Lincomycin fungi residues lincomycin residual quantity be 1200~1500mg/kg, pH=4.16.
9. the method that a kind of utilization lincomycin fungi residues according to claim 1 produce organic fertilizer, it is characterised in that described
Lincomycin fungi residues lincomycin residual quantity be 1200~1300mg/kg, pH=4.16.
10. the method that a kind of utilization lincomycin fungi residues according to claim 9 produce organic fertilizer, it is characterised in that described
Lincomycin fungi residues lincomycin residual quantity be 1200~1400mg/kg, pH=4.16.
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| CN110041142A (en) * | 2019-05-31 | 2019-07-23 | 上海化工研究院有限公司 | A method of amino acid Water soluble fertilizer is prepared using antibiotic fermentation waste residue |
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Application publication date: 20171103 |