CN102344220B - Method for treating metronidazole waste water - Google Patents
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- CN102344220B CN102344220B CN 201110202387 CN201110202387A CN102344220B CN 102344220 B CN102344220 B CN 102344220B CN 201110202387 CN201110202387 CN 201110202387 CN 201110202387 A CN201110202387 A CN 201110202387A CN 102344220 B CN102344220 B CN 102344220B
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- waste water
- formic acid
- metronidazole
- anhydrous sodium
- sodium sulphate
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- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229960000282 metronidazole Drugs 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 60
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 48
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019253 formic acid Nutrition 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 30
- 235000011152 sodium sulphate Nutrition 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000004280 Sodium formate Substances 0.000 abstract 3
- 239000005416 organic matter Substances 0.000 abstract 3
- 235000019254 sodium formate Nutrition 0.000 abstract 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- PPSMYAUEJRADFE-HXUWFJFHSA-N 2-[(5r)-4-[2-[3-(6-methylpyridin-3-yl)oxyphenyl]acetyl]-8-(trifluoromethyl)-1,2,3,5-tetrahydropyrido[2,3-e][1,4]diazepin-5-yl]acetic acid Chemical compound C1=NC(C)=CC=C1OC1=CC=CC(CC(=O)N2[C@@H](C3=CC=C(N=C3NCC2)C(F)(F)F)CC(O)=O)=C1 PPSMYAUEJRADFE-HXUWFJFHSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WGRQANOPCQRCME-PMACEKPBSA-N teneligliptin Chemical compound O=C([C@H]1NC[C@H](C1)N1CCN(CC1)C1=CC(=NN1C=1C=CC=CC=1)C)N1CCSC1 WGRQANOPCQRCME-PMACEKPBSA-N 0.000 description 1
- FWQHRZXEQNUCSY-UHFFFAOYSA-N tert-butyl N-[2-(ethoxycarbonylamino)-5-[(4-fluorophenyl)methyl-prop-2-ynylamino]phenyl]carbamate Chemical compound CCOC(=O)NC1=C(C=C(C=C1)N(CC#C)CC2=CC=C(C=C2)F)NC(=O)OC(C)(C)C FWQHRZXEQNUCSY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for treating metronidazole waste water, which comprises the following steps of: concentrating the metronidazole waste water into 1/3-1/5 of total amount, and crystallizing and filtering the concentrated metronidazole waste water at 45-100 DEG C to obtain anhydrous sodium sulfate and sodium formate; adjusting the PH to 3-6 by using sulfuric acid or formic acid, and precipitating 2-methy-5-nitro imidazole; concentrating the filter liquid to anhydrous sticky state, dissolving organic matter by using methanol or ethanol, and filtering the solution to obtain anhydrous sodium sulfate and sodium formate; merging the sodium formate and the anhydrous sodium sulfate obtained in two times, successively adding formic acid and sulfuric acid, and recovering the formic acid to obtain anhydrous sodium sulfate; and rectifying and separating the organic mixture extract of methanol or ethanol to obtain methanol or ethanol and glycol. The method for treating metronidazole waste water provided by the invention is simple and convenient to operate, the content of polluting organic matter and inorganic slats in the metronidazole waste water can be obviously reduced, environmental pollution can be preveneted, various kinds of useful organic matter and inorganic matter can be recovered, raw materials are saved, and the production cost is lowered.
Description
Technical field
The present invention relates to a kind for the treatment of process of metronidazole waste water, belong to Industrial Wastewater Treatment and recovery technology field.
Background technology
Development along with medicine industry, the waste water that produces in the pharmacy procedure has become one of serious source of pollution, owing to need use plurality of raw materials at medicine production process, complex manufacturing, water quality, the water yield fluctuate larger, and waste water composition is very complicated, is one of larger trade effluent of intractability, the microbiotic trade effluent in the pharmacy waste water particularly is a class high chroma, contain hard-degraded substance and the many high concentrated organic wastewaters of bio-toxicity material.
Metronidazole is a kind of microbiotic bulk drug that extensively adopts in the medication chemistry industry, mainly adopts polymerization, oxidation, the chemical process such as nitrated, makes organic raw material produce required medicine intermediate and synthesis material medicine through chemical reaction.All kinds of organic raw material of a large amount of uses in the production process, through polystep reaction, complex process, the raw material and the reaction product that contain multiple not complete reaction in the metronidazole waste water, comprise the raw materials such as 2-5-nitro imidazole, and the pollutent such as other organism, salt (sodium sulfate that produces in the production technique).If the organism in the waste water directly discharges, easily cause the eutrophication of water body, decomposite multiple obnoxious flavour, not only cause the serious water pollution also can polluted air; A large amount of inorganic salt can make water pH value change in the waste water, destroy its natural shock absorption, elimination or anti-bacteria and microbial growth, hinder self-purification of waters, can greatly increase water hardness simultaneously, cause salting of soil, all bring disadvantageous effect for industry and life.
But these organism and inorganic salts also have important utility value simultaneously.For example, contained organic itrated compound can be used as and produces the medical material intermediate in the waste water; Anhydrous sodium sulphate is widely used in the fields such as chemical alkaline, papermaking and glass industry; Formic acid is widely used in the industrial circles such as agricultural chemicals, leather, dyestuff, medicine and rubber manufacturing.Therefore, not only cause environmental pollution if will contain the direct discharging of a large amount of organic itrated compounds and inorganic salt, or a kind of very large waste.
Summary of the invention
The waste water that the present invention is directed to existing metronidazole production process generation contains multiple organism and salt with high pollution, directly discharging causes the pollution to environment, and multiple useful matter does not obtain the problem of effective recycling, a kind for the treatment of process of metronidazole factory effluent is provided, significantly reduce the organism of contaminative in the metronidazole waste water and the content of inorganic salts, make the metronidazole waste water after the processing reach discharging standards, can be to environment, and can reclaim itrated compound, formic acid, the multiple useful organism such as sodium sulfate and inorganics, economize in raw materials, reduce production costs, and treatment process is simple, easy to operate.
The present invention for realizing the technical scheme that technical purpose adopts is:
A kind for the treatment of process of metronidazole waste water may further comprise the steps:
(1) metronidazole waste water is revolved the 1/5-1/3 that inspissation is reduced to the volume total amount, then anhydrous sodium sulphate and sodium formiate are filtered to get in crystallization under 45 ℃ of-100 ℃ of temperature;
(2) with step (1) gained filtrate with sulfuric acid or first acid for adjusting pH value to pH3-6, separate out, filter and obtain 2-5-nitro imidazole crystal;
(3) step (2) gained filtrate being revolved inspissation again is reduced to anhydrous thick, press the mass ratio 1:0.25 of enriched product and solvent～0.35 and add the anhydrous methanol solvent, under 30 ℃ of-50 ℃ of temperature, make enriched product dissolving 0.5-2 hour, filter to get anhydrous sodium sulphate and sodium formiate;
(4) with step (1) and step (3) gained anhydrous sodium sulphate and the merging of sodium formiate mixture, press the mass ratio 1:0.3 of mixture and formic acid～1 and add formic acid, make the dissolving of anhydrous sodium sulphate and sodium formiate, 1/2 proportioning by contained sodium formiate mole number slowly adds the vitriol oil again, 60 ℃-120 ℃ lower reactions 0.5-3 hour, reclaim formic acid, obtain formic acid and anhydrous sodium sulphate;
(5) the mother liquor rectifying separation after step (3) filtration is obtained methyl alcohol and ethylene glycol.
A kind for the treatment of process of metronidazole waste water, metronidazole waste water are the waste water of metronidazole crude product after centrifugal.
The mass concentration of dissolving anhydrous sodium sulphate and the used formic acid of sodium formiate is 88% in a kind for the treatment of process of metronidazole waste water, described step (4), and the formic acid mass concentration of recovery is 88.5%～90%.
The itrated compound that can reclaim from metronidazole waste water according to the method described above is the 2-5-nitro imidazole, intermediate mainly as medicine production, the anhydrous sodium sulphate that recovery obtains, formic acid, methyl alcohol or ethanol and ethylene glycol are realized recycle mainly as industrial chemicals.
Advantage of the present invention and beneficial effect are:
1. contain multiple pollutant in the metronidazole factory effluent; but be important industrial chemicals simultaneously; by processing and the recovery to the metronidazole factory effluent; prevent that not only direct discharging of waste water is to environment; protection of the environment; can also realize recovery and the recycle of multiple important industrial chemicals, economize in raw materials, reduce production costs.
2. utilize sodium sulfate and sodium formiate under specified temp in methyl alcohol, alcohol solvent the little chemical property of solubleness, use methyl alcohol, ethanol to make solvent, under specified temp, fast sodium sulfate and sodium formiate are separated out and are reclaimed, organic efficiency is high, cost recovery is low.
3. the boiling point of methyl alcohol or ethanol and ethylene glycol is lower, and rectifying can be isolated methyl alcohol, ethanol and ethylene glycol from filtrate under differing temps, methyl alcohol or ethanol can be recycled, and significantly saves processing cost.
4. whole treatment process reaction conditions is gentle, operation is simple, with low cost.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
Get metronidazole crude product centrifuge waste water 1200ml, put in the 2L flask, revolve steaming to remaining 400ml solution, anhydrous sodium sulphate and sodium formiate are filtered to get in crystallization under 55 ℃ of temperature, dry to get 106.3g.Filtrate is regulated pH=5 with sulfuric acid and is separated out itrated compound 9g, stirs filtering drying under the room temperature.Then filtrate is revolved inspissation again and is reduced to the thick solution of 280g, and the anhydrous methanol that adds 280g after 1.5 hours, filters to get anhydrous sodium sulphate and sodium formiate 40 ℃ of lower reactions, dries to get 145g.Twice anhydrous sodium sulphate and sodium formiate are merged (analyzing to such an extent that the content of sodium formiate is 37.42%), add first 70g content and be 88% formic acid and make its dissolving, slowly add again the 73g strong sulfuric acid response, keep temperature of reaction after the reaction 100 ℃ of reactions 1 hour, reclaim under reduced pressure obtains formic acid 130g (content is 88.9%), anhydrous sodium sulphate 220g.To obtain methyl alcohol 226g and ethylene glycol 35g by separation under the extract rectifier unit of methyl alcohol.
Embodiment 2:
Get metronidazole crude product centrifuge waste water 1200ml, put in the 2L flask, revolve steaming to remaining 300ml solution, crystallization under 45 ℃ of temperature is filtered to get anhydrous sodium sulphate and sodium formiate with enriched material, dries to get 115g.Filtrate is regulated pH=3 with sulfuric acid and is separated out itrated compound 8g, stirs filtering drying under the room temperature.Then filtrate is revolved inspissation again and is reduced to the thick solution of 271g, adds 30 ℃ of lower reactions of anhydrous methanol of 406.5g after 2 hours, filters to get anhydrous sodium sulphate and sodium formiate, dries to get 145g.Twice anhydrous sodium sulphate and sodium formiate are merged (analyzing to such an extent that the content of sodium formiate is 37.69%), add first 80g content and be 88% formic acid and make its dissolving, slowly add again the 77g strong sulfuric acid response, keep after the reaction temperature of reaction 60 ℃ the reaction 3 hours, it is 89.2% that reclaim under reduced pressure obtains formic acid 143g(content), anhydrous sodium sulphate 240g.The extract of methyl alcohol is obtained methyl alcohol 337g and ethylene glycol 37g by separation under rectifier unit.
Embodiment 3:
Get metronidazole crude product centrifuge waste water 1200ml, put in the 2L flask, revolve steaming to remaining 240ml solution, crystallization under 100 ℃ of temperature is filtered to get anhydrous sodium sulphate and sodium formiate with enriched material, dries to get 124g.Filtrate is regulated pH=6 with sulfuric acid and is separated out itrated compound 10g, stirs filtering drying under the room temperature.Then filtrate is revolved inspissation again and is reduced to the thick solution of 260g, adds 50 ℃ of lower reactions of anhydrous methanol of 650g after 0.5 hour, filters to get anhydrous sodium sulphate and sodium formiate, dries to get 143g.Twice anhydrous sodium sulphate and sodium formiate are merged (analyzing to such an extent that the content of sodium formiate is 38.11%), add first 90g content and be 88% formic acid and make its dissolving, the strong sulfuric acid response that slowly adds again 80g, keep temperature of reaction after the reaction 120 ℃ of reactions 0.5 hour, it is 89.5% that reclaim under reduced pressure obtains formic acid 155g(content), get anhydrous sodium sulphate 255g.The extract of methyl alcohol is obtained methyl alcohol 552g and ethylene glycol 40g by separation under rectifier unit.
Claims (3)
1. the treatment process of a metronidazole waste water is characterized in that may further comprise the steps:
(1) metronidazole waste water is revolved the 1/5-1/3 that inspissation is reduced to the volume total amount, then anhydrous sodium sulphate and sodium formiate are filtered to get in crystallization under 45 ℃ of-100 ℃ of temperature;
(2) with step (1) gained filtrate with sulfuric acid or first acid for adjusting pH value to pH3-6, separate out, filter and obtain 2-5-nitro imidazole crystal;
(3) step (2) gained filtrate being revolved inspissation again is reduced to anhydrous thick, press the mass ratio 1:1 of enriched product and solvent～2.5 and add the anhydrous methanol solvents, under 30 ℃ of-50 ℃ of temperature, make enriched product dissolving 0.5-2 hour, filter to get anhydrous sodium sulphate and sodium formiate;
(4) with step (1) and step (3) gained anhydrous sodium sulphate and the merging of sodium formiate mixture, press the mass ratio 1:0.25 of mixture and formic acid～0.35 and add formic acid, make the dissolving of anhydrous sodium sulphate and sodium formiate, 1/2 proportioning by contained sodium formiate mole number slowly adds the vitriol oil again, 60 ℃-120 ℃ lower reactions 0.5-3 hour, reclaim formic acid, obtain formic acid and anhydrous sodium sulphate;
(5) the mother liquor rectifying separation after step (3) filtration is obtained methyl alcohol and ethylene glycol.
2. the treatment process of a kind of metronidazole waste water according to claim 1 is characterized in that: metronidazole waste water is the waste water of metronidazole crude product after centrifugal.
3. the treatment process of a kind of metronidazole waste water according to claim 1 is characterized in that: the mass concentration of dissolving anhydrous sodium sulphate and the used formic acid of sodium formiate is 88% in the described step (4), and the formic acid mass concentration of recovery is 88.5%～90%.
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| CN 201110202387 CN102344220B (en) | 2011-07-19 | 2011-07-19 | Method for treating metronidazole waste water |
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| CN 201110202387 CN102344220B (en) | 2011-07-19 | 2011-07-19 | Method for treating metronidazole waste water |
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| CN102344220B true CN102344220B (en) | 2013-03-27 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898297B (en) * | 2012-09-18 | 2014-06-04 | 湖北省宏源药业有限公司 | Processing method of metronidazole industrial waste mixed salt |
| CN104030507B (en) * | 2013-03-04 | 2016-07-06 | 黄冈银河阿迪药业有限公司 | Biogas thermal source processes metronidazole and produces the ecological circulation technology of waste water |
| CN104072424A (en) * | 2013-03-29 | 2014-10-01 | 黄冈师范学院 | Environmental novel co-production technology of metronidazole and composite fertilizer |
| CN103408082B (en) * | 2013-08-10 | 2014-12-03 | 黄冈师范学院 | Recovery method and device for formic acid solvent in metronidazole production process |
| CN103483265B (en) * | 2013-09-05 | 2015-07-15 | 湖北省宏源药业科技股份有限公司 | Metronidazole production method |
| CN103880235A (en) * | 2014-04-16 | 2014-06-25 | 湖北省宏源药业有限公司 | Treatment method for dimetronidazole production wastewater |
| CN103922532B (en) * | 2014-04-29 | 2015-10-07 | 宁夏东吴农化有限公司 | Imidazolidine tail washings treatment process |
| CN105776707B (en) * | 2016-04-25 | 2021-04-27 | 湖北省宏源药业科技股份有限公司 | Metronidazole wastewater treatment method |
| CN107325054A (en) * | 2017-07-17 | 2017-11-07 | 黄冈师范学院 | The method of accessory substance recycled in metronidazole production process |
| CN109179745A (en) * | 2018-08-29 | 2019-01-11 | 杭州轩辉环境设备有限公司 | A kind for the treatment of process for the waste water producing fatty acid generation |
| CN112777612A (en) * | 2020-12-31 | 2021-05-11 | 赤峰迪生药业有限责任公司 | AE active ester etherification wastewater treatment method |
| CN117820233B (en) * | 2023-12-13 | 2025-02-11 | 河北广祥制药有限公司 | A method for recovering materials from metronidazole crude product mother liquor |
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| DE68904070T2 (en) * | 1989-05-09 | 1993-04-29 | Bayer Antwerpen Nv | METHOD FOR REMOVING NITRATE AND ORGANIC IMPURITIES FROM SEWAGE. |
| CN101560188B (en) * | 2009-05-26 | 2011-05-04 | 武汉工程大学 | Method for separating and purifying 2-methylimidazole crystal impurity |
| CN101914062B (en) * | 2010-09-01 | 2011-12-07 | 中南民族大学 | Method for recovering metronidazole finished product from industrial waste residue of metronidazole |
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Denomination of invention: Method for treating metronidazole waste water Effective date of registration: 20140509 Granted publication date: 20130327 Pledgee: Huanggang SME investment Company Limited by Guarantee Pledgor: Hubei Hongyuan Pharmaceutical Co., Ltd. Registration number: 2014420000005 |
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Address after: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee after: HUBEI HONGYUAN PHARMACEUTICAL TECHNOLOGY CO., LTD. Address before: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee before: Hubei Hongyuan Pharmaceutical Co., Ltd. |
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Date of cancellation: 20150728 Granted publication date: 20130327 Pledgee: Huanggang SME investment Company Limited by Guarantee Pledgor: Hubei Hongyuan Pharmaceutical Co., Ltd. Registration number: 2014420000005 |
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Denomination of invention: A treatment method of metronidazole wastewater Effective date of registration: 20220512 Granted publication date: 20130327 Pledgee: Industrial and Commercial Bank of China Limited Luotian sub branch Pledgor: HUBEI HONGYUAN PHARMACEUTICAL TECHNOLOGY Co.,Ltd. Registration number: Y2022420000116 |
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