CN103012312A - Method for recycling industrial wastewater of aminothiazoly loximate - Google Patents
Method for recycling industrial wastewater of aminothiazoly loximate Download PDFInfo
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- CN103012312A CN103012312A CN2012105123973A CN201210512397A CN103012312A CN 103012312 A CN103012312 A CN 103012312A CN 2012105123973 A CN2012105123973 A CN 2012105123973A CN 201210512397 A CN201210512397 A CN 201210512397A CN 103012312 A CN103012312 A CN 103012312A
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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 the 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)-the 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, the steps such as halogenation, cyclization and hydrolysis obtain product.By the research to production system waste water, find to produce a large amount of waste water in the explained hereafter, but the major part reuse in system of this type of waste water by processing wastewater is optimized processing, realizes that the quantity discharged of waste water reduces, and has improved simultaneously the yield of reaction product.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 dissolving Sodium Nitrite, realize oximate with the reaction of three second under acidic conditions, the adding purified water was carried out extracting and demixing, discharge of wastewater to reaction product after oximate was finished.
Methylate:
Utilize pure water dissolving soda ash, in methanol solution, drip dimethyl ester, add purified water after reaction finishes reaction product is carried out extracting and demixing, discharge of wastewater.
Hydrolysis:
Add the deionized water dissolving cyclized ester, use liquid caustic soda, carry out basic hydrolysis, reaction is finished and is neutralized to pH with hydrochloric acid is 6.5-7.0, centrifugation, filtrate discharge; Product pure water drip washing, the washing water discharging
Summary of the invention
The method that the purpose of this invention is to provide the reuse of a kind of ainothiazoly loximate factory effluent improves product yield, reduces the processing wastewater quantity discharged, has preferably economic benefit and environmental benefit.
The method of ainothiazoly loximate factory effluent of the present invention reuse becomes oximate into single step reaction and the recycle of hydrolysis rear filtrate with methylating, and concrete steps are as follows:
Oximate and methylating
With hydrolysis treatment water dissolution Sodium Nitrite, under acidic conditions, realize oximate with methyl aceto acetate and catalyst reaction, after oximate finishes, add the soda ash dissolving, add again methyl alcohol and methyl-sulfate, layering after reaction finishes, the reaction product in the extraction wastewater, extraction liquid and the recycle of organic phase Distillation recovery extraction agent are discharged behind the waste water reclamation solvent;
Hydrolysis
Regulate pH after adding the 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 get drying products, and the filtrate of centrifugation and washing water get back in the oximation reaction recycling after regulating pH.
Described catalyzer is dilute sulphuric acid.
Described extraction agent is chloroform or methylene dichloride.
Methylate after the end, organic phase underpressure distillation to extraction agent steams fully, then carries out halogenation and ring-closure reaction.Wherein, the preferential chlorine of halogenating agent, halogenated products is stand-by.The ring-closure reaction step is to add damping fluid and cyclization reagent in methyl alcohol, is stirred to fully dissolving.Slowly at the uniform velocity drip halogenated products, temperature control drips off rear adjusting pH between 25-32 ℃, 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; Helping discoloring agent is 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 ℃.
Compared with prior art, the present invention has following beneficial effect:
Because oximate and methylating is become cycling utilization of wastewater after single step reaction and the hydrolysis, reduce the product that discharge of wastewater is taken away, simultaneously because the product in the extraction wastewater, in the waste water product meltage still less, product yield was from originally the highest 74% bringing up to more than 80%.Processing wastewater discharging after the improvement has reduced 67%.Have preferably economic benefit and environmental benefit.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
1. add hydrolysis treatment water 1800L in reactor, add Sodium Nitrite 263Kg again, stirring is fully dissolved it.After adding the 450Kg methyl aceto acetate, slow dilute sulphuric acid 60Kg at the uniform velocity, temperature control drips 4 hours at 8 ℃.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to 16 ℃, add 910L methyl alcohol again, uniform speed slow drips methyl-sulfate 600Kg again, and temperature control drips off rear insulation 4 hours.Left standstill layering 30 minutes; Add the 200Kg chloroform, stirred 30 minutes, left standstill layering 30 minutes; Add the 200Kg chloroform in the organic phase again, stirred 30 minutes, left standstill 30 minutes, separatory discharges 1800L behind the waste water reclamation solvent.Organic phase underpressure distillation to chloroform steams fully, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to fully dissolving.Slowly at the uniform velocity drip halogenide, temperature control drips off rear adjusting pH and is 6.8 at 32 ℃, and is centrifugal, methyl alcohol drip washing.
3. with 1500L deionized water dissolving cyclized ester, 40 ℃ of liquid caustic soda that slowly drip 200L of temperature control stirred 7 hours, and material is fully dissolved.Transfer pH: transfer pH to 7.0 with hydrochloric acid, add EDTA, S-WAT, gac decoloured 1 hour.Suction filtration 2 times, filtrate are cooled to 20 ℃, and transferring pH with hydrochloric acid is 2.2, mixes up rear insulation, centrifugal, uses pure water drip washing.Filtrate and the washing water of centrifugation are regulated pH to 7.5 with liquid caustic soda, get back in the oximation reaction recycling.The filter residue oven dry gets dry qualified product 601Kg.
Embodiment 2
1. add hydrolysis treatment water 1900L in reactor, add Sodium Nitrite 263Kg again, stirring is fully dissolved it.After adding the 450Kg methyl aceto acetate, slow dilute sulphuric acid 60Kg at the uniform velocity, temperature control drips 4.2 hours at 10 ℃.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to below 16 ℃, add 910L methyl alcohol again, uniform speed slow drips methyl-sulfate 600Kg again, and temperature control drips off rear insulation 4 hours.Left standstill layering 30 minutes; Add the 200Kg chloroform, stirred 30 minutes, left standstill layering 30 minutes; Add the 200Kg methylene dichloride in the organic phase again, stirred 30 minutes, left standstill 30 minutes, separatory discharges 1900L behind the waste water reclamation solvent.Organic phase underpressure distillation to methylene dichloride steams fully, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to fully dissolving.Slowly at the uniform velocity drip halogenide, temperature control drips off rear adjusting pH and is 7.0 at 30 ℃, and is centrifugal, methyl alcohol drip washing.
3. with 1600L deionized water dissolving cyclized ester, 42 ℃ of liquid caustic soda that slowly drip 200L of temperature control stirred 7.4 hours, and material is fully dissolved.Transfer pH: transfer pH to 6.8 with hydrochloric acid, add diatomite 50Kg, decoloured 1 hour.Suction filtration 2 times, filtrate are cooled to 20 ℃, and transferring pH with hydrochloric acid is 2.4, mixes up rear insulation, centrifugal, uses pure water drip washing.Filtrate and the washing water of centrifugation are regulated pH to 7.2 with liquid caustic soda, get back in the oximation reaction.The filter residue oven dry gets dry qualified product 586Kg.
Embodiment 3
1. add hydrolysis treatment water 1800L in reactor, add Sodium Nitrite 263Kg again, stirring is fully dissolved it.After adding the 450Kg methyl aceto acetate, slow dilute sulphuric acid 60Kg at the uniform velocity, temperature control drips 4.5 hours at 14 ℃.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to below 16 ℃, add 910L methyl alcohol again, uniform speed slow drips methyl-sulfate 600Kg again, and temperature control drips off rear insulation 4 hours.Left standstill layering 30 minutes; Add the 200Kg chloroform, stirred 30 minutes, left standstill layering 30 minutes; Add the 200Kg chloroform in the organic phase again, stirred 30 minutes, left standstill 30 minutes, separatory discharges 1800L behind the waste water reclamation solvent.Organic phase underpressure distillation to chloroform steams fully, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to fully dissolving.Slowly at the uniform velocity drip halogenide, temperature control drips off rear adjusting pH and is 6.5 at 27 ℃, and is centrifugal, methyl alcohol drip washing.
3. with 1500L deionized water dissolving cyclized ester, 45 ℃ of liquid caustic soda that slowly drip 200L of temperature control stirred 7.8 hours, and material is fully dissolved.Transfer pH: transfer pH to 6.7 with hydrochloric acid, add diatomite 50Kg, decoloured 40 minutes.Suction filtration 2 times, filtrate are cooled to 20 ℃, and transferring pH with hydrochloric acid is 2.3, mixes up rear insulation, centrifugal, uses pure water drip washing.Filtrate and the washing water of centrifugation are regulated pH to 7.0 with liquid caustic soda, get back in the oximation reaction.The filter residue oven dry gets dry qualified product 597Kg.
Embodiment 4,
1. add hydrolysis treatment water 1800L in reactor, add Sodium Nitrite 263Kg again, stirring is fully dissolved it.After adding the 450Kg methyl aceto acetate, slow dilute sulphuric acid 60Kg at the uniform velocity, temperature control drips 4.1 hours at 11 ℃.In still, add 300Kg soda ash, stir.After soda ash fully dissolves, be cooled to 16 ℃, add 910L methyl alcohol again, uniform speed slow drips methyl-sulfate 600Kg again, and temperature control drips off rear insulation 4 hours.Left standstill layering 30 minutes; Add the 200Kg chloroform, stirred 30 minutes, left standstill layering 30 minutes; Add the 200Kg methylene dichloride in the organic phase again, stirred 30 minutes, left standstill 30 minutes, separatory discharges 1800L behind the waste water reclamation solvent.Organic phase underpressure distillation to methylene dichloride steams fully, carries out halogenation.Halogenated products is stand-by.
2. in 1530L methyl alcohol, add sodium-acetate 450Kg, thiocarbamide 225Kg, be stirred to fully dissolving.Slowly at the uniform velocity drip halogenide, temperature control drips off rear adjusting pH and is 7.0 at 25 ℃, and is centrifugal, methyl alcohol drip washing.
3. with 1500L deionized water dissolving cyclized ester, 40 ℃ of liquid caustic soda that slowly drip 200L of temperature control stirred 8 hours, and material is fully dissolved.Transfer pH: transfer pH to 7.0 with hydrochloric acid, add gac 50Kg, decoloured 1.5 hours.Suction filtration 2 times, filtrate are cooled to 20 ℃, and transferring pH with hydrochloric acid is 2.5, mixes up rear insulation, centrifugal, uses pure water drip washing.Filtrate and the washing water of centrifugation are regulated pH to 7.3 with liquid caustic soda, get back in the oximation reaction.The filter residue oven dry gets dry qualified product 579Kg.
Claims (7)
1. the method for ainothiazoly loximate factory effluent reuse is characterized in that, oximate is become single step reaction and the recycle of hydrolysis rear filtrate with methylating, and concrete steps are as follows:
Oximate and methylating
With hydrolysis treatment water dissolution Sodium Nitrite, under acidic conditions, realize oximate with the methyl aceto acetate reaction, after oximate finishes, add the soda ash dissolving, add again methyl alcohol and methyl-sulfate, layering after reaction finishes, the reaction product in the extraction wastewater, extraction liquid and the recycle of organic phase Distillation recovery extraction agent are discharged behind the waste water reclamation solvent;
Hydrolysis
Regulate pH after adding the deionized water dissolving cyclized ester, add complexing agent, help discoloring agent and discoloring agent, then carry out suction filtration, centrifugal; After the filter residue drip washing oven dry, get drying products, filtrate gets back in the oximation reaction recycling after regulating pH.
2. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, extraction agent is chloroform or methylene dichloride.
3. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, discoloring agent is diatomite, silica gel, molecular sieve or gac.
4. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, the temperature of dissolving cyclized ester is 40-45 ℃.
5. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, complexing agent is EDTA; Helping discoloring agent is S-WAT.
6. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, the hydrolysis bleaching time is 0.5-2 hour.
7. according to the method for claims 1 described ainothiazoly loximate factory effluent reuse, it is characterized in that, the filtrate pH regulator of centrifugation is 7.0-7.5 after the hydrolysis.
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Cited By (6)
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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 |
| CN110790721A (en) * | 2019-12-06 | 2020-02-14 | 山东金城医药化工有限公司 | Synthetic method of ceftazidime side chain ethyl ester |
| CN111548323A (en) * | 2020-05-29 | 2020-08-18 | 山东金城医药化工有限公司 | Recovery method of aminothiazoly loximate |
| CN112661719A (en) * | 2020-12-22 | 2021-04-16 | 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 |
| CN113023988A (en) * | 2021-03-10 | 2021-06-25 | 湖南海利常德农药化工有限公司 | Method for treating methomyl process wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111548323A (en) * | 2020-05-29 | 2020-08-18 | 山东金城医药化工有限公司 | Recovery method of aminothiazoly loximate |
| 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 |
| CN112661719A (en) * | 2020-12-22 | 2021-04-16 | 河北合佳医药科技集团股份有限公司 | Clean preparation process 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 |
| CN113023988A (en) * | 2021-03-10 | 2021-06-25 | 湖南海利常德农药化工有限公司 | Method for treating methomyl process wastewater |
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