CN102627581B - Preparation process of N-phenylglycinonitrile - Google Patents
Preparation process of N-phenylglycinonitrile Download PDFInfo
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- CN102627581B CN102627581B CN 201210073895 CN201210073895A CN102627581B CN 102627581 B CN102627581 B CN 102627581B CN 201210073895 CN201210073895 CN 201210073895 CN 201210073895 A CN201210073895 A CN 201210073895A CN 102627581 B CN102627581 B CN 102627581B
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Abstract
The invention relates to a preparation technology of N-phenylglycinonitrile with the characteristics of economy and environmental protection, and especially provides a technology for mother liquid utilization and wastewater processing in the production of N-phenylglycinonitrile. The preparation technology comprises operations of condensation reaction mother liquid recovery processing, N-phenylglycinonitrile is obtained by carrying out the condensation reaction on aniline, hydroxyacetonitrile and a catalyst in the presence of water (or the mother liquid), the content is greater than 97%, the liquid phase purity is greater than 97%, N-phenylglycinonitrile is a colorless or light yellow transparent crystal, and the yield is greater than 99.5%. The resulting reacted mother liquid can be directly reused in the condensation operation without processing, almost all organic matters can be recovered through physically processing exhaustless wastewater, COD of residual wastewater is less than 200ppm, and the total nitrogen content in the residual wastewater is less than 50ppm. By adopting above optimized technology, the ammonia nitrogen content is reduced, and the COD is reduced, so 75-90% of the mother liquid can be recycled to the condensation reaction and can be repeatedly reused, thereby the wastewater processing amount is reduced; and additionally, the recycle of the mother liquid makes the organic matters in the mother liquid be fully recovered, and yield improvement and cost saving be realized.
Description
Technical field
The present invention relates to a kind of environmental protection preparation technology who produces the N-aniline-acetonitrile with hydroxyacetonitrile, belong to the preparing technical field of N-aniline-acetonitrile.
Background technology
The N-aniline-acetonitrile is indigo main raw material, and the method for synthetic N-aniline-acetonitrile has following several:
1. sodium cyanide method: number of patent application CN971045054.0 discloses a kind of " N-phenylglycine salt manufacturing process ", adopts aniline, sodium cyanide, formaldehyde, under magnesium salts (magnesium chloride or sal epsom) exists, generates the N-aniline-acetonitrile.
2. prussic acid method: German patent DE 3010511,2621450,2621728,2625935, Japanese Patent JP591210052,56141251, employing aniline, formaldehyde, liquid (gas) prussic acid such as Chinese patent CN02113428.6 are raw material, and add auxiliary agent, obtain the N-aniline-acetonitrile through reaction, crystallization, yield 80-95.2%, content 92-98%.
3. hydroxyacetonitrile method: English Patent BP1119256, it is raw material that Chinese patent CN200910103536.5 adopts hydroxyacetonitrile, aniline, auxiliary agent, through pipe reaction, obtains the N-aniline-acetonitrile, yield 99.8%, content is more than 95.5%.
Sodium cyanide method has been used the highly toxic substance sodium cyanide, and the prussic acid method has been used prussic acid, and equipment is had to severe corrosive, and the equipment making precision is high, and operant level requires meticulous, and facility investment is larger, is unsuitable for serialization scale operation.The hydroxyacetonitrile method has overcome above-mentioned defect, but its produce COD in waste water, BOD content is high, and the aniline that contains a great deal of, prussiate and nitrogen, need to carry out wastewater treatment, its production cost is high.
Wastewater treatment for the hydroxyacetonitrile method, (the Pre-treatment of Wastewater Extracted from N-phenylglycinenitrile experimental study such as Li Chaowei, " China environmental protection industry ", in November, 2007) reported and a kind ofly take benzene as extraction agent, keep the pH value of former water constant, be in a ratio of 0.33, after three stage countercurrent extraction treatment, the percentage extraction of aniline, total chloride, ammonia nitrogen and COD reaches respectively 91%, 93%, 42% and 52%, has improved the biodegradability of waste water.But the method has been used highly toxic substance benzene, is unfavorable for industrialization.
Introduced the condensation reaction of aniline and hydroxyacetonitrile in CN200810016883.x " a kind of method for making of environment-friendly type aniline-acetonitrile ", also having introduced the reuse of mother liquor and the Physiochemical and biochemical of mother liquor processes, but its mother liquor reclamation rate is low, only has 12-20%, in addition, its wastewater treatment process complexity, equipment is many, and processing cost is higher.
Therefore, in the production method of N-aniline-acetonitrile, the hydroxyacetonitrile method is comparatively general at present, but needs to find the production technique of a kind of more economy and environmental protection.
Summary of the invention
The present invention is mainly the deficiency for the synthetic N-aniline-acetonitrile of above-mentioned hydroxyacetonitrile method, provide a kind of more economically, the N-aniline-acetonitrile preparation technology of environmental protection more, utilization and the wastewater treatment of mother liquor in a kind of production of N-aniline-acetonitrile especially are provided.N-aniline-acetonitrile environmental protection preparation technology, comprise condensation reaction operation and mother liquor recycling operation, it is characterized in that:
1. described condensation reaction is aniline, hydroxyacetonitrile, catalyzer condensation reaction under the existence of water (or mother liquor), and the weight ratio of each raw material is: aniline: hydroxyacetonitrile: water (mother liquor): catalyzer=1: 1.20-1.5: 0.5-5: 0-0.001.10%-60% hydroxyacetonitrile stream is added in the mixture of aniline and water (or mother liquor), then 70--90 ℃ of reaction 0.5-3 hour, then by temperature, is elevated to reposefully between 90--110 ℃ and reacts 1-6 hour.Then progressively be cooled to 30-50 ℃ of crystallization, the 15-40 ℃ of centrifugal N-aniline-acetonitrile that obtains, content is greater than 97%, and liquid phase purity is greater than 97%, colourless or light yellow transparent crystals, yield is more than 99.5%.
2. described mother liquor is without processing direct reuse condensation operation, exhaustless waste water reclaims most organism through physical treatment, the residue waste water COD is less than 200ppm, total nitrogen is less than 50ppm, pH 7-9, can after activated carbon decolorizing, with mineral acid, neutralize pH is 7 discharges, and mineral acid is commonly used hydrochloric acid, sulfuric acid etc.
Above-mentioned reacting middle catalyst can add also and can not add, as long as the pH of water (or mother liquor) can not add catalyzer in the 8-12 scope, catalyzer is alkaline matter: organic basic material and inorganic base substance all can; Organic bases is preferably the aminated compoundss such as triethylamine, N.N-dimethyl formamide, and the metal-salt of the alcohols such as sodium methylate, potassium ethylate, more preferably triethylamine and sodium methylate, mineral alkali is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, ammoniacal liquor etc., more preferably ammoniacal liquor and sodium hydroxide.
Can be all or part of mother liquor that replaces with of water in above-mentioned reaction;
In above-mentioned reaction, the weight ratio of each raw material is preferred: aniline: hydroxyacetonitrile: water (mother liquor)=1: 1.25-1.3: 3.5-4;
The preferred 50-55% hydroxyacetonitrile of hydroxyacetonitrile in above-mentioned reaction;
In above-mentioned reaction, mother liquor waste water can pass through physical treatment, utilize organism that certain viscosity is arranged, by 1 grade--5 grades of organism enriching apparatus (seeing Fig. 2), Recycling Mother Solution, organic matter will form foam and rises in enricher, thereby organic will overflow being enriched in the upper groove of enricher, thereby reach the separating organic matters inrichment.Preferred 3-5 level organism enriching apparatus, the reuse of getting up of organism enrichment in mother liquor waste water, residue waste water can neutralize discharge, the preferred toluene of organic substance extraction solvent for use, methylene dichloride;
Mother liquor direct reuse condensation operation in above-mentioned reaction, reaction soln can all be applied mechanically mother liquor, and the mother liquor reclamation rate is high, and treatment capacity is few, and the environmental protection treatment expense is lower.
Beneficial effect
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts the N-aniline-acetonitrile production technique of optimization, adopts excessive hydroxyacetonitrile in above-mentioned technique, makes aniline reaction complete, and in mother liquor, ammonia-nitrogen content reduces, and COD reduces; Simultaneously, the consumption of catalyzer reduces greatly, makes aftertreatment easier, the more easily separated recovery of organism.Adopt above-mentioned Optimization Technology, ammonia-nitrogen content reduces, and COD reduces, and the mother liquor that makes 75-90% all retraction capable of circulation closes in reaction, and repeatedly reuse repeatedly, has reduced wastewater treatment capacity; Mother liquid recycling, can fully reclaim the organism in mother liquor in addition, improves yield, cost-saving;
2. the N-aniline-acetonitrile that the present invention produces, yield and the quality level that all is in a leading position, production cost is lower;
3. the present invention adopts organism enriching apparatus of the prior art, realizes the mother liquid disposal serialization, the waste water after processing can be directly in and qualified discharge, processing costs is extremely low;
4. technique of the present invention has thoroughly solved the processing problem of factory effluent, is the technique of clean environment firendly, has good social benefit.
The accompanying drawing explanation
The accompanying drawing 1N-aniline-acetonitrile technological process of production
Accompanying drawing 2 organism enriching apparatus
Preferred forms
Embodiment 1:
Add 200g distilled water in the 500ml four-hole bottle, the ammoniacal liquor 2g with 25% regulates pH to 11, then adds 99.5% aniline 50g, stir, then in 5min, add 50% hydroxyacetonitrile 65g, be heated to 70-75 ℃ of reaction 0.5h, then temperature is elevated to 90-95 ℃ of reaction 6h reposefully.Then progressively be cooled to 40-45 ℃ of crystallization, the 15-20 ℃ of centrifugal N-aniline-acetonitrile that obtains, content 97.05%, liquid phase purity 97.12%, colourless transparent crystal, yield 99.50%.
Obtain mother liquor waste water 240g, COD35000ppm, total nitrogen 2000ppm, pH value 11, described mother liquor waste water can be after 3 grades of organism enriching apparatus (toluene is extraction agent), mother liquor waste water COD reduces to 128ppm, total nitrogen is reduced to 46ppm, and the pH value is 9, through the activated carbon decolorizing 0.5h of mother liquor amount 1%, being filtered into colourless liquid, is 7 rear discharges with the salt acid for adjusting pH value.The organic mother liquor 100g that obtained enrichment, reclaim and use.
Embodiment 2:
Add 200g mother liquor and 135g distilled water in the 1000ml four-hole bottle, survey pH and be 10 and need not regulate, then add 99.5% aniline 95g, stir, then in 5min, add 50% hydroxyacetonitrile 119g, be heated to 70-75 ℃ of reaction 1h, then temperature is elevated to 95-98 ℃ of reaction 4h reposefully.Then progressively be cooled to 45-48 ℃ of crystallization, the 20-25 ℃ of centrifugal N-aniline-acetonitrile that obtains, content 97.35%, liquid phase purity 97.54%, micro-yellow transparent crystal, yield 99.81%.
Obtain mother liquor waste water 380g, COD25000ppm, total nitrogen 1500ppm, pH value 9.5, described mother liquor waste water can be after 4 grades of organism enriching apparatus (methylene dichloride is extraction agent), mother liquor waste water COD reduces to 155ppm, total nitrogen is reduced to 40ppm, and the pH value is 8, through the activated carbon decolorizing 0.5h of mother liquor amount 0.5%, being filtered into colourless liquid, is 7 rear discharges with the salt acid for adjusting pH value.The organic mother liquor 120g that obtained enrichment, reclaim and use.
Embodiment 3:
Add the 535g mother liquor in the 1000ml four-hole bottle, survey pH and be 9 and need not regulate, add thereafter 99.5% aniline 100g, stir, then in 5min, add 50% hydroxyacetonitrile 127g, be heated to 70-75 ℃ of reaction 1.5h, then temperature is elevated to 95-98 ℃ of reaction 2h reposefully.Then progressively be cooled to 35-40 ℃ of crystallization, the 25-30 ℃ of centrifugal N-aniline-acetonitrile that obtains, content 97.65%, liquid phase purity 97.70%, micro-yellow transparent crystal, yield 99.88%.
Obtain mother liquor waste water 560g, COD30000ppm, total nitrogen 1600ppm, pH value 8.5, described mother liquor waste water can be after 5 grades of organism enriching apparatus (toluene is extraction agent), mother liquor waste water COD reduces to 130ppm, total nitrogen is reduced to 42ppm, and the pH value is 8, through the activated carbon decolorizing 0.5h of mother liquor amount 0.5%, being filtered into colourless liquid, is 7 rear discharges with the salt acid for adjusting pH value.The organic mother liquor 180g that obtained enrichment, reclaim and use.
Embodiment 4:
Organism and water of 130g of adding the enrichment of 200g mother liquor in the 1000ml four-hole bottle, surveying pH and be 10.5 need not regulate, thereafter add 99.5% aniline 95g, stir, then in 5min, add 50.5% hydroxyacetonitrile 119g, be heated to 70-75 ℃ of reaction 1h, then temperature is elevated to 90-98 ℃ of reaction 3.5h reposefully.Then progressively be cooled to 40-48 ℃ of crystallization, the 20-25 ℃ of centrifugal N-aniline-acetonitrile that obtains, content 97.65%, liquid phase purity 97.74%, micro-yellow transparent crystal, yield 99.99%.
Obtain mother liquor waste water 370g, COD26000ppm, total nitrogen 1650ppm, pH value 10, described mother liquor waste water can be after 5 grades of organism enriching apparatus (toluene is extraction agent), mother liquor waste water COD reduces to 100ppm, total nitrogen is reduced to 35ppm, and the pH value is 9, through the activated carbon decolorizing 0.5h of mother liquor amount 0.5%, being filtered into colourless liquid, is 7 rear discharges with the salt acid for adjusting pH value.The organic mother liquor 90g that obtained enrichment, reclaim and use.
Embodiment 5:
Add the 5500kg mother liquor in the 12500L reactor, surveying pH and be 9.5 need not regulate, then add 99.5% aniline 1000kg, stir, then in 20min, add 51% hydroxyacetonitrile 1270kg, be heated to 70-75 ℃ of reaction 1.5h, then temperature is elevated to reposefully between 95-98 ℃ and reacts 4h.Then progressively be cooled to 35-40 ℃ of crystallization, the 30-35 ℃ of centrifugal N-aniline-acetonitrile that obtains, content 97.45%, liquid phase purity 97.56%, micro-yellow transparent crystal, yield 99.95%.
Obtain mother liquor waste water 5900kg, COD28500ppm, total nitrogen 1650ppm, pH value 9, the 5500kg mother liquor directly returns cover, residue mother liquor waste water 400kg can be after 5 grades of organism enriching apparatus (methylene dichloride is extraction agent), and mother liquor waste water COD reduces to 80ppm, and total nitrogen is reduced to 135ppm, the pH value is 8.5, activated carbon decolorizing 0.5h through mother liquor amount 0.5%, be filtered into colourless liquid, with the salt acid for adjusting pH value, is 7 rear discharges.The organic mother liquor 95Kg that obtained enrichment, reclaim and use.
Above-described embodiment is only explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (4)
1.N-the preparation technology of aniline-acetonitrile, comprise condensation reaction operation and mother liquor recycling operation, it is characterized in that:
(1) described condensation reaction is aniline, hydroxyacetonitrile, catalyzer condensation reaction under the existence of water or mother liquor, and the weight ratio of each raw material is: aniline: hydroxyacetonitrile: water or mother liquor: catalyzer=1:1.25-1.3:3.5-4:0-0.001; The 10%-60% hydroxyacetonitrile is added in the mixture of aniline and water or mother liquor, then 70-90 ℃ of reaction 0.5-3 hour, then by temperature, is elevated to reposefully between 90-110 ℃ and reacts 1-6 hour; Then progressively be cooled to 30-50 ℃ of crystallization, the 15-40 ℃ of centrifugal N-aniline-acetonitrile that obtains, content is greater than 97%, and liquid phase purity is greater than 97%, colourless or light yellow transparent crystals, yield is more than 99.5%;
Wherein catalyzer is ammoniacal liquor;
When raw material mother liquor pH is greater than 8, do not add catalyzer;
(2) mother liquor that above-mentioned condensation reaction produces is without processing direct reuse to the condensation operation, and exhaustless mother liquor reclaims organism and uses 1 grade--5 grades of organism enriching apparatus, and recovery solvent used is toluene or methylene dichloride; The residue waste water COD is less than 100ppm, and total nitrogen is less than 50ppm, pH7-9, and neutralizing pH with mineral acid after activated carbon decolorizing is 7 discharges.
2. the preparation technology of N-aniline-acetonitrile according to claim 1, is characterized in that in described reaction all or part of mother liquor that replaces with of water.
3. N-aniline-acetonitrile preparation technology according to claim 1 and 2, is characterized in that the hydroxyacetonitrile that described raw material hydroxyacetonitrile concentration is 50-55%.
4. N-aniline-acetonitrile preparation technology according to claim 1, is characterized in that in described reaction, mineral acid is hydrochloric acid or sulfuric acid.
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| CN104628601A (en) * | 2015-01-30 | 2015-05-20 | 广安诚信化工有限责任公司 | Preparation method of efficient environmental-friendly aniline acetonitrile |
| CN104671375A (en) * | 2015-01-30 | 2015-06-03 | 广安诚信化工有限责任公司 | Method for processing N-phenylglycinenitrile mother solution |
| CN104910032B (en) * | 2015-03-20 | 2017-06-23 | 重庆紫光化工股份有限公司 | A kind of preparation method of anilino-acetate |
| CN104788340B (en) * | 2015-03-20 | 2016-09-28 | 重庆紫光化工股份有限公司 | A kind of preparation method of aniline-acetonitrile |
| CN104725273B (en) * | 2015-04-16 | 2017-03-01 | 重庆紫光化工股份有限公司 | A kind of aniline-acetonitrile novel crystal forms and preparation method thereof |
| CN104725272B (en) * | 2015-04-16 | 2016-06-29 | 重庆紫光化工股份有限公司 | A kind of preparation method of aniline-acetonitrile |
| CN104761467A (en) * | 2015-04-17 | 2015-07-08 | 重庆紫光化工股份有限公司 | Anilino acetonitrile synthesis method |
| CN109535028B (en) * | 2018-11-15 | 2021-10-08 | 天津科技大学 | Method for preparing pure anilinoacetonitrile by suspension melting crystallization method |
| CN109748820B (en) * | 2019-01-22 | 2021-11-30 | 重庆紫光化工股份有限公司 | System and method for preparing anilinoacetonitrile |
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| CN101613306B (en) * | 2008-06-24 | 2013-09-11 | 淄博齐田医药化工有限公司 | Method for preparing environment-friendly aniline-acetonitrile |
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Inventor after: Zhang Chenliang Inventor after: Li Juan Inventor after: Liu Xu Inventor after: Yao Liguo Inventor after: Wang Shuoshuo Inventor after: Wang Shaodan Inventor after: Chen Yongze Inventor after: Cheng Lihua Inventor after: Peng Yanli Inventor after: Qu Yongjuan Inventor before: Zhang Chenliang Inventor before: Li Yushun Inventor before: Cheng Lihua Inventor before: Yin Junli Inventor before: Wang Xuehua |
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Effective date of registration: 20180705 Address after: 750336 Inner Mongolia Alxa League Alashan Economic Development Zone, the north end of Lantai Road Patentee after: Inner Mongolia integrity Yong'an Chemical Co., Ltd. Address before: 051130 Yuanshi County, Shijiazhuang, Hebei Province, yuan Zhao Lu Patentee before: Hebei Chengxin Co., Ltd. |