CN103012312B - Method for recycling industrial wastewater of aminothiazoly loximate - Google Patents
Method for recycling industrial wastewater of aminothiazoly loximate Download PDFInfo
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- CN103012312B CN103012312B CN201210512397.3A CN201210512397A CN103012312B CN 103012312 B CN103012312 B CN 103012312B CN 201210512397 A CN201210512397 A CN 201210512397A CN 103012312 B CN103012312 B CN 103012312B
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Abstract
The invention discloses a method for recycling industrial wastewater of aminothiazoly loximate, which belongs to the field of wastewater recovery. According to the method provided by the invention, oximation and methylation are integrated. The method comprises the steps of: oximation and methylation: dissolving sodium nitrite by hydrolytic treatment water, carrying out reaction with ethyl acetoacetate under an acidic condition, adding soda ash, methanol and dimethyl sulfate after oximation, layering after reaction, extracting reaction products in wastewater, distilling and recovering extract liquor and an organic phase for recycle, and discharging wastewater after recovering the solvent; hydrolysis: adding deionized water to dissolve cyclized ester and adjusting pH, adding a complexing agent, a decolorising assistant agent and a decolorising agent, and then filtering and centrifugalizing; washing and drying filter residue to obtain a dried product, wherein filtrate and washing water after centrifugal separation return to oximation reaction for recycle. According to the method provided by the invention, products brought by wastewater discharged are reduced, and the product yield is greatly improved. According to modified process wastewater discharge, the method has better economical benefit and environment-friendly benefit.
Description
Technical field
The invention belongs to waste water reclamation field, be specifically related to the method for a kind of ainothiazoly loximate factory effluent reuse.
Background technology
Ainothiazoly loximate is white or off-white color crystalline powder.English name: Thiazoximic acid; Chemical name: 2-(2-amino-4-thiazolyl)-2-methoxyimino Acetic Acid; Molecular formula: C
6h
7n
3o
3s, molecular weight: 201.2; Chemical structure:
General domestic production methyl aceto acetate be raw material by oximate, methylate, halogenation, the step such as cyclization and hydrolysis obtain product.By the research to production system waste water, find to produce a large amount of waste water in explained hereafter, this type of waste water in systems in which major part can reuse, and by being optimized process to processing wastewater, the quantity discharged realizing waste water reduces, and improves the yield of reaction product simultaneously.Chemical equation:
In traditional technology, oximate, methylate, the step such as hydrolysis is the key link that waste water produces, main technique is as follows:
Oximate:
Utilize pure water to dissolve Sodium Nitrite, react with three second in acid condition and realize oximate, add purified water after oximate completes and extracting and demixing is carried out to reaction product, discharge of wastewater.
Methylate:
Utilize pure water to dissolve soda ash, in methanol solution, drip dimethyl ester, add purified water after reaction terminates and extracting and demixing is carried out to reaction product, discharge of wastewater.
Hydrolysis:
Add deionized water dissolving cyclized ester, with liquid caustic soda, carry out basic hydrolysis, reacted that to be neutralized to pH with hydrochloric acid be 6.5-7.0, centrifugation, filtrate discharge; Product pure water drip washing, washing water discharges
Summary of the invention
The object of this invention is to provide the method for a kind of ainothiazoly loximate factory effluent reuse, improve product yield, reduce processing wastewater quantity discharged, there is good economic benefit and environmental benefit.
The method of ainothiazoly loximate factory effluent of the present invention reuse, oximate is become single step reaction and the rear filtrate cycle utilization of hydrolysis with methylating, and concrete steps are as follows:
Oximate and methylating
With hydrolysis treatment water dissolution Sodium Nitrite, oximate is realized in acid condition with methyl aceto acetate and catalyst reaction, after oximate terminates, add soda ash to dissolve, add methyl alcohol and methyl-sulfate again, reaction terminates rear layering, the reaction product in extraction wastewater, extraction liquid and the recycle of organic phase Distillation recovery extraction agent, discharge after waste water reclamation solvent;
Hydrolysis
Regulate pH after adding deionized water dissolving cyclized ester, add complexing agent, help discoloring agent and discoloring agent, then carry out suction filtration and centrifugal; Filter residue drip washing, oven dry, obtain drying products, after the filtrate of centrifugation and washing water regulate pH, gets back in oximation reaction and recycle.
Described catalyzer is dilute sulphuric acid.
Described extraction agent is chloroform or methylene dichloride.
Methylate after terminating, organic phase underpressure distillation steams completely to extraction agent, then carries out halogenation and ring-closure reaction.Wherein, the preferential chlorine of halogenating agent, halogenated products is stand-by.Ring-closure reaction step, for add damping fluid and cyclization reagent in methyl alcohol, is stirred to and dissolves completely.Slowly at the uniform velocity drip halogenated products, temperature control, between 25-32 DEG C, drips off rear adjustment pH, centrifugal, uses methyl alcohol drip washing.Wherein, damping fluid is sodium-acetate; Cyclization reagent thiocarbamide.
Described discoloring agent is diatomite, silica gel, molecular sieve or gac.
Described complexation of metal ions is EDTA; Discoloring agent is helped to be S-WAT.
Described hydrolysis bleaching time is 0.5-2 hour.
Described washing water is 7.0-7.5 with the pH regulator of filtrate.
The temperature of described dissolving cyclized ester is 40-45 DEG C.
Compared with prior art, the present invention has following beneficial effect:
Owing to oximate and methylating to be become cycling utilization of wastewater after single step reaction and hydrolysis, reduce the product that discharge of wastewater is taken away, simultaneously due to the product in extraction wastewater, in waste water, product meltage is less, and product yield brought up to more than 80% from original the highest 74%.Processing wastewater discharge after improvement decreases 67%.There is good economic benefit and environmental benefit.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1. add hydrolysis treatment water 1800L in a kettle., then add Sodium Nitrite 263Kg, stir and make it fully dissolve.After adding 450Kg methyl aceto acetate, slowly at the uniform velocity dilute sulphuric acid 60Kg, temperature control, at 8 DEG C, drips 4 hours.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to 16 DEG C, then add 910L methyl alcohol, then uniform speed slow drips methyl-sulfate 600Kg, temperature control, drips off rear insulation 4 hours.Leave standstill 30 minutes, layering; Add 200Kg chloroform, stir 30 minutes, leave standstill 30 minutes, layering; Add 200Kg chloroform again in organic phase, stir 30 minutes, leave standstill 30 minutes, separatory, discharges 1800L after waste water reclamation solvent.Organic phase underpressure distillation steams completely to chloroform, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to and dissolve completely.Slowly at the uniform velocity drip halogenide, temperature control is at 32 DEG C, and dripping off rear adjustment pH is 6.8, centrifugal, methyl alcohol drip washing.
3., with 1500L deionized water dissolving cyclized ester, temperature control 40 DEG C slowly drips the liquid caustic soda of 200L, stirs 7 hours, material is fully dissolved.Adjust pH: adjust pH to 7.0 with hydrochloric acid, add EDTA, S-WAT, gac, decolour 1 hour.Suction filtration 2 times, filtrate is cooled to 20 DEG C, adjusts pH to be 2.2, mix up rear insulation with hydrochloric acid, centrifugal, uses pure water drip washing.The filtrate of centrifugation and washing water liquid caustic soda are regulated pH to 7.5, gets back in oximation reaction and recycle.Filter residue is dried, and obtains dry qualified product 601Kg.
Embodiment 2
1. add hydrolysis treatment water 1900L in a kettle., then add Sodium Nitrite 263Kg, stir and make it fully dissolve.After adding 450Kg methyl aceto acetate, slowly at the uniform velocity dilute sulphuric acid 60Kg, temperature control, at 10 DEG C, drips 4.2 hours.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to less than 16 DEG C, then add 910L methyl alcohol, then uniform speed slow drips methyl-sulfate 600Kg, temperature control, drips off rear insulation 4 hours.Leave standstill 30 minutes, layering; Add 200Kg chloroform, stir 30 minutes, leave standstill 30 minutes, layering; Add 200Kg methylene dichloride again in organic phase, stir 30 minutes, leave standstill 30 minutes, separatory, discharges 1900L after waste water reclamation solvent.Organic phase underpressure distillation steams completely to methylene dichloride, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to and dissolve completely.Slowly at the uniform velocity drip halogenide, temperature control is at 30 DEG C, and dripping off rear adjustment pH is 7.0, centrifugal, methyl alcohol drip washing.
3., with 1600L deionized water dissolving cyclized ester, temperature control 42 DEG C slowly drips the liquid caustic soda of 200L, stirs 7.4 hours, material is fully dissolved.Adjust pH: adjust pH to 6.8 with hydrochloric acid, add diatomite 50Kg, decolour 1 hour.Suction filtration 2 times, filtrate is cooled to 20 DEG C, adjusts pH to be 2.4, mix up rear insulation with hydrochloric acid, centrifugal, uses pure water drip washing.The filtrate of centrifugation and washing water liquid caustic soda are regulated pH to 7.2, gets back in oximation reaction.Filter residue is dried, and obtains dry qualified product 586Kg.
Embodiment 3
1. add hydrolysis treatment water 1800L in a kettle., then add Sodium Nitrite 263Kg, stir and make it fully dissolve.After adding 450Kg methyl aceto acetate, slowly at the uniform velocity dilute sulphuric acid 60Kg, temperature control, at 14 DEG C, drips 4.5 hours.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to less than 16 DEG C, then add 910L methyl alcohol, then uniform speed slow drips methyl-sulfate 600Kg, temperature control, drips off rear insulation 4 hours.Leave standstill 30 minutes, layering; Add 200Kg chloroform, stir 30 minutes, leave standstill 30 minutes, layering; Add 200Kg chloroform again in organic phase, stir 30 minutes, leave standstill 30 minutes, separatory, discharges 1800L after waste water reclamation solvent.Organic phase underpressure distillation steams completely to chloroform, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to and dissolve completely.Slowly at the uniform velocity drip halogenide, temperature control is at 27 DEG C, and dripping off rear adjustment pH is 6.5, centrifugal, methyl alcohol drip washing.
3., with 1500L deionized water dissolving cyclized ester, temperature control 45 DEG C slowly drips the liquid caustic soda of 200L, stirs 7.8 hours, material is fully dissolved.Adjust pH: adjust pH to 6.7 with hydrochloric acid, add diatomite 50Kg, decolour 40 minutes.Suction filtration 2 times, filtrate is cooled to 20 DEG C, adjusts pH to be 2.3, mix up rear insulation with hydrochloric acid, centrifugal, uses pure water drip washing.The filtrate of centrifugation and washing water liquid caustic soda are regulated pH to 7.0, gets back in oximation reaction.Filter residue is dried, and obtains dry qualified product 597Kg.
Embodiment 4,
1. add hydrolysis treatment water 1800L in a kettle., then add Sodium Nitrite 263Kg, stir and make it fully dissolve.After adding 450Kg methyl aceto acetate, slowly at the uniform velocity dilute sulphuric acid 60Kg, temperature control, at 11 DEG C, drips 4.1 hours.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to 16 DEG C, then add 910L methyl alcohol, then uniform speed slow drips methyl-sulfate 600Kg, temperature control, drips off rear insulation 4 hours.Leave standstill 30 minutes, layering; Add 200Kg chloroform, stir 30 minutes, leave standstill 30 minutes, layering; Add 200Kg methylene dichloride again in organic phase, stir 30 minutes, leave standstill 30 minutes, separatory, discharges 1800L after waste water reclamation solvent.Organic phase underpressure distillation steams completely to methylene dichloride, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to and dissolve completely.Slowly at the uniform velocity drip halogenide, temperature control is at 25 DEG C, and dripping off rear adjustment pH is 7.0, centrifugal, methyl alcohol drip washing.
3., with 1500L deionized water dissolving cyclized ester, temperature control 40 DEG C slowly drips the liquid caustic soda of 200L, stirs 8 hours, material is fully dissolved.Adjust pH: adjust pH to 7.0 with hydrochloric acid, add gac 50Kg, decolour 1.5 hours.Suction filtration 2 times, filtrate is cooled to 20 DEG C, adjusts pH to be 2.5, mix up rear insulation with hydrochloric acid, centrifugal, uses pure water drip washing.The filtrate of centrifugation and washing water liquid caustic soda are regulated pH to 7.3, gets back in oximation reaction.Filter residue is dried, and obtains dry qualified product 579Kg.
Claims (1)
1. a method for ainothiazoly loximate factory effluent reuse, is characterized in that, preparation process is as follows:
(1) add hydrolysis treatment water 1800L in a kettle., then add Sodium Nitrite 263Kg, stir and make it fully dissolve, after adding 450Kg methyl aceto acetate, slowly at the uniform velocity add dilute sulphuric acid 60Kg, temperature control is at 8 DEG C, drip 4 hours, in still, add 300Kg soda ash, stir, after soda ash fully dissolves, be cooled to 16 DEG C, then add 910L methyl alcohol, uniform speed slow drips methyl-sulfate 600Kg again, and temperature control, drips off rear insulation 4 hours, leave standstill 30 minutes, layering; Add 200Kg chloroform, stir 30 minutes, leave standstill 30 minutes, layering; Add 200Kg chloroform again in organic phase, stir 30 minutes, leave standstill 30 minutes, separatory, discharges 1800L after waste water reclamation solvent, and organic phase underpressure distillation steams completely to chloroform, and carry out halogenation, halogenated products is stand-by;
(2) in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225 Kg, be stirred to and dissolve completely, slowly at the uniform velocity drip halogenide, temperature control is at 32 DEG C, and dripping off rear adjustment pH is 6.8, centrifugal, methyl alcohol drip washing;
(3) with 1500 L deionized water dissolving cyclized esters, temperature control 40 DEG C slowly drips the liquid caustic soda of 200L, stir 7 hours, material is fully dissolved, adjust pH: adjust pH to 7.0 with hydrochloric acid, add EDTA, S-WAT, gac, decolours 1 hour, suction filtration 2 times, filtrate is cooled to 20 DEG C, adjusts pH to be 2.2, mix up rear insulation with hydrochloric acid, centrifugal, use pure water drip washing, the filtrate of centrifugation and washing water liquid caustic soda are regulated pH to 7.5, gets back in oximation reaction and recycle, filter residue is dried, and obtains dry qualified product 601Kg.
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| CN105502296A (en) * | 2015-12-29 | 2016-04-20 | 河北合佳医药科技集团有限公司 | Method for preparing bromine from bromine-containing waste water produced during production of aminothiazoly loximate |
| CN110790721B (en) * | 2019-12-06 | 2021-10-22 | 山东金城医药化工有限公司 | Synthetic method of ceftazidime side chain ethyl ester |
| CN111548323B (en) * | 2020-05-29 | 2022-06-10 | 山东金城医药化工有限公司 | Recovery method of aminothiazoly loximate |
| CN112661719B (en) * | 2020-12-22 | 2022-10-14 | 河北合佳医药科技集团股份有限公司 | Clean preparation process of aminothiazoly loximate |
| 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 |
| CN113023988B (en) * | 2021-03-10 | 2022-08-12 | 湖南海利常德农药化工有限公司 | Method for treating methomyl process wastewater |
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| JP2845789B2 (en) * | 1995-12-25 | 1999-01-13 | 株式会社トクヤマ | Method for producing aminothiazoleacetic acid derivative |
| IT1295935B1 (en) * | 1997-10-30 | 1999-05-28 | Acs Dobfar Spa | AMINOTHIAZOLE DERIVATIVES USEFUL IN THE PREPARATION OF B-LACTAMICS ANTIBIOTICS |
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Denomination of invention: Method for reusing wastewater from aminothiaoxime acid production Effective date of registration: 20211216 Granted publication date: 20150506 Pledgee: Commercial Bank of China Yiyuan branch of Limited by Share Ltd. Pledgor: SHANDONG XINQUAN PHARMACEUTICAL Co.,Ltd. Registration number: Y2021980015208 |
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Date of cancellation: 20220721 Granted publication date: 20150506 Pledgee: Commercial Bank of China Yiyuan branch of Limited by Share Ltd. Pledgor: SHANDONG XINQUAN PHARMACEUTICAL Co.,Ltd. Registration number: Y2021980015208 |