CN108117500B - Method for reducing waste water and waste salt generated in amination process in production process of methyl sulfamate - Google Patents
Method for reducing waste water and waste salt generated in amination process in production process of methyl sulfamate Download PDFInfo
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- CN108117500B CN108117500B CN201711193677.1A CN201711193677A CN108117500B CN 108117500 B CN108117500 B CN 108117500B CN 201711193677 A CN201711193677 A CN 201711193677A CN 108117500 B CN108117500 B CN 108117500B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a method for reducing waste water and waste salt generated in an amination process in a production process of methyl sulfamate. The method for reducing the waste salt of the wastewater generated by the amination process in the production process of the methyl sulfamate has the advantages of simple process, fewer steps and easiness in operation and control, most of ammonia gas is expelled by adopting a blowing method after the amination reaction, residues are neutralized and acidified by using a small amount of hydrochloric acid, and the expelled ammonia water is absorbed by a spray tower and then is applied to the follow-up batch amination reaction, so that the waste salt of the wastewater is effectively reduced, the energy is saved, the environment is protected, and the economic benefit is good.
Description
Technical Field
The invention belongs to the technical field of drug synthesis processes, and particularly relates to a method for reducing waste salt in wastewater generated by an amination process in a production process of sulfamethazine.
Background
In the production process of sulpiride intermediate methyl sulfamate, a large amount of ammonia water is used in the ammonification reaction process, the original post-treatment is acid-adjusting crystallization, a large amount of waste water and waste salt can be generated, great trouble is brought to the post-treatment, not only is resource waste caused, but also the production cost is improved, a large amount of environmental pollution is generated, and the use requirement cannot be met.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide the method for reducing the waste salt of the wastewater generated by the amination process in the production process of the methyl sulfamate, and the method has the advantages of simple method, less steps, effective reduction of the waste salt of the wastewater and the like.
The technical scheme is as follows: in order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for reducing waste salt of wastewater generated by an amination process in a production process of methyl sulfamate comprises the following steps: after the ammoniation reaction is finished, most of ammonia gas is blown out of the reaction kettle by a blowing method, the ammonia gas is recycled, residues are neutralized and acidified by a small amount of hydrochloric acid, and waste water and waste salt are reduced.
The method for reducing the waste salt of the wastewater generated by the amination process in the production process of the methyl sulfamate is characterized in that at least 70% of ammonia gas is blown out of the reaction kettle by adopting a blowing method.
According to the method for reducing the waste salt of the wastewater generated in the amination process in the production process of the methyl sulfamate, the blown ammonia gas is absorbed by the spray tower and then is recycled for the amination reaction of the subsequent batch.
The ammoniation reaction comprises the following steps:
I) ammonia water with the concentration of 25 percent is put into an ammoniation kettle;
II) opening a cooling water inlet valve and a cooling water return valve, slowly adding benzoyl under stirring, controlling the temperature to be below 20 ℃, and covering a feed port to prevent ammonia gas from overflowing after the benzoyl is added;
III) closing a cooling water inlet valve and a cooling water return valve, slowly opening a steam inlet valve and a steam return valve, keeping the temperature in the kettle at 70-75 ℃ for about 1.5 hours, removing ammonia by a blowing method after the reaction is finished, and recycling the ammonia gas through a spray tower; after ammonia removal is finished, closing the steam inlet valve and the steam return valve, and opening the cooling water inlet valve and the cooling water return valve to reduce the reaction temperature to 30 +/-2 ℃;
IV) opening a vacuum pump, sucking hydrochloric acid, then adding hydrochloric acid into the reaction liquid to adjust the pH value to 1.0-1.5, and controlling the acid adding speed to ensure that the temperature does not exceed 50 ℃; after the acid precipitation is finished, heating the temperature to 98 +/-2 ℃, preserving the temperature for 15 minutes, continuing stirring to reduce the temperature of the reaction liquid to normal temperature, stopping stirring, closing a cooling water valve, returning the cooling water valve, and standing for 2 hours;
v) after standing, starting centrifugation, washing a filter cake to pH 3-4 by using drinking water, breaking the filter cake, putting the filter cake in an oven, and drying for 22 hours at 83-87 ℃ to obtain the amide.
In the ammoniation reaction, the mass ratio of benzoyl to 25% ammonia water is 1: 1.7.
has the advantages that: compared with the prior art, the method for reducing the waste salt of the wastewater generated by the amination process in the production process of the methyl sulfamate has the advantages of simple process, few steps, easiness in operation and control, most of ammonia gas is expelled by adopting a blowing method after the amination reaction, residues are neutralized and acidified by using a small amount of hydrochloric acid, and the expelled ammonia water is absorbed by a spray tower and then is applied to the follow-up batch of amination reaction, so that the waste salt of the wastewater is effectively reduced, the energy is saved, the environment is protected, and the economic benefit is good.
Detailed Description
The present invention will be further illustrated by the following specific examples, which are carried out on the premise of the technical scheme of the present invention, and it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
A method for reducing waste water and waste salt generated in an amination process in a production process of methyl sulfamate comprises the following steps:
1. preparation of 2-methoxy-5-sulfamoylbenzoic acid (amide for short)
The raw material ratio is as follows: 1Kg of benzoyl and 1.7Kg of 25% ammonia water.
The ammoniation reaction comprises the following steps:
I) 25 percent of ammonia water with the absorption and proportioning quantity is put into an ammoniation kettle.
II) opening a cooling water inlet valve and a cooling water return valve, slowly adding benzoyl under stirring, controlling the temperature to be below 20 ℃, and covering a feed port to prevent ammonia gas from overflowing after the benzoyl is added.
III) closing a water inlet and return cooling valve, slowly opening a steam inlet valve and a steam return valve, keeping the temperature in the kettle at 70-75 ℃ for about 1.5 hours, removing ammonia by a blowing method after the reaction is finished, and recycling the ammonia gas through a spray tower. And (5) closing the steam inlet valve and the steam return valve after ammonia removal is finished, and opening the cooling water inlet valve and the cooling water return valve to reduce the reaction temperature to 30 +/-2 ℃.
IV) opening a vacuum pump, sucking hydrochloric acid, adding hydrochloric acid into the reaction liquid to adjust the pH value to 1.0-1.5, and controlling the acid adding speed to be preferably not more than 50 ℃. And (3) after the acid precipitation is finished, raising the temperature to 98 +/-2 ℃, preserving the temperature for 15 minutes, continuing stirring to reduce the temperature of the reaction liquid to the normal temperature, stopping stirring, closing the cooling water valve, returning the cooling water valve, and standing for 2 hours (the water valve can be slightly opened and returned, and the standing temperature is kept at 25-35 ℃).
V) after standing, starting centrifugation, washing a filter cake to pH 3-4 by using drinking water, breaking the filter cake, putting the filter cake in an oven, and drying for 22 hours at 83-87 ℃ to obtain the amide. The yield is 65-75%.
Analysis of the reduction: 2mol of ammonia is consumed for 1mol of benzoyl in the ammoniation reaction, the amount of ammonia consumed for 1kg of benzoyl is 0.136kg, the actual amount of ammonia added is 0.425kg, and the ammonia is greatly excessive. The amount of waste ammonium chloride generated by the direct acid adjustment treatment according to the post-treatment was 0.91kg, the amount of waste ammonium chloride generated after the actual blowing was 0.273kg, and 637kg of waste salt was reduced by performing the ammonification of 1t of benzoyl.
The annual amount of the sulfamethazine of the applicant is more than or equal to 100t, the process can reduce 55t of waste salt every year, reduce 14.3 ten thousand yuan of waste salt landfill cost, and reduce the consumption of hydrochloric acid, and the blowing process has great benefits for environmental protection and cost reduction.
Claims (4)
1. A method for reducing waste water and waste salt generated in an amination process in a production process of methyl sulfamate is characterized by comprising the following steps: after the ammoniation reaction is finished, most of ammonia gas is blown out of the reaction kettle by adopting a blowing method, the ammonia gas is recycled and reused, and residues are neutralized and acidified by using a small amount of hydrochloric acid, so that waste water and waste salt are reduced; the ammoniation reaction comprises the following steps:
I) ammonia water with the concentration of 25 percent is put into an ammoniation kettle;
II) opening a cooling water inlet valve and a cooling water return valve, slowly adding benzoyl under stirring, controlling the temperature to be below 20 ℃, and covering a feed port to prevent ammonia gas from overflowing after the benzoyl is added;
III) closing a cooling water inlet valve and a cooling water return valve, slowly opening a steam inlet valve and a steam return valve, keeping the temperature in the kettle at 70-75 ℃ for about 1.5 hours, removing ammonia by a blowing method after the reaction is finished, and recycling the ammonia gas through a spray tower; after ammonia removal is finished, closing the steam inlet valve and the steam return valve, and opening the cooling water inlet valve and the cooling water return valve to reduce the reaction temperature to 30 +/-2 ℃;
IV) opening a vacuum pump, sucking hydrochloric acid, then adding hydrochloric acid into the reaction liquid to adjust the pH value to 1.0-1.5, and controlling the acid adding speed to ensure that the temperature does not exceed 50 ℃; after the acid precipitation is finished, heating the temperature to 98 +/-2 ℃, preserving the temperature for 15 minutes, continuing stirring to reduce the temperature of the reaction liquid to normal temperature, stopping stirring, closing a cooling water valve, returning the cooling water valve, and standing for 2 hours;
v) after standing, beginning centrifugation, washing a filter cake to pH 3-4 with drinking water, crushing the filter cake, placing the filter cake in an oven, and drying the filter cake for 22 hours at 83-87 ℃ to obtain an amide; the amide is 2-methoxy-5-sulfamoylbenzoic acid.
2. The method for reducing the waste salt of wastewater generated in the amination process in the production process of methyl sulfamate according to claim 1, wherein at least 70% of ammonia gas is blown out of the reaction kettle by a blowing method.
3. The method for reducing the waste salt of the wastewater generated in the amination process in the production process of the methyl sulfamate according to claim 1, wherein the blown ammonia gas is absorbed by the spray tower and then is recycled for the amination reaction of the subsequent batch.
4. The method for reducing the waste salt of wastewater generated by an amination reaction process in the production process of methyl sulfamate according to claim 1, wherein the mass ratio of benzoyl to 25% ammonia water is 1: 1.7.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320997A (en) * | 2011-08-05 | 2012-01-18 | 丁同富 | Para-acetylsulfanilamide synthesis method combined with waste water treatment |
| CN102659277A (en) * | 2012-05-10 | 2012-09-12 | 杭州蓝然环境技术有限公司 | Ammonium fluoride wastewater treatment technique |
| CN103318918A (en) * | 2013-05-14 | 2013-09-25 | 武汉百富环保工程有限公司 | Method for purification and recovery of ammonia gas |
| CN203469550U (en) * | 2013-08-20 | 2014-03-12 | 中芯国际集成电路制造(北京)有限公司 | Liquid waste disposal device |
| CN104672114A (en) * | 2013-11-26 | 2015-06-03 | 门修信 | A preparing method of 2,4-dichloro-5-sulfamoylbenzoic acid |
| CN104725282A (en) * | 2014-07-17 | 2015-06-24 | 叶良梅 | Novel environment-friendly production process of 1-naphthol-4-sulfonic acid |
| CN105017098A (en) * | 2015-07-17 | 2015-11-04 | 大连奇凯医药科技有限公司 | Preparation technology of alkyloxybenzsulfamide and its derivatives |
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- 2017-11-24 CN CN201711193677.1A patent/CN108117500B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320997A (en) * | 2011-08-05 | 2012-01-18 | 丁同富 | Para-acetylsulfanilamide synthesis method combined with waste water treatment |
| CN102659277A (en) * | 2012-05-10 | 2012-09-12 | 杭州蓝然环境技术有限公司 | Ammonium fluoride wastewater treatment technique |
| CN103318918A (en) * | 2013-05-14 | 2013-09-25 | 武汉百富环保工程有限公司 | Method for purification and recovery of ammonia gas |
| CN203469550U (en) * | 2013-08-20 | 2014-03-12 | 中芯国际集成电路制造(北京)有限公司 | Liquid waste disposal device |
| CN104672114A (en) * | 2013-11-26 | 2015-06-03 | 门修信 | A preparing method of 2,4-dichloro-5-sulfamoylbenzoic acid |
| CN104725282A (en) * | 2014-07-17 | 2015-06-24 | 叶良梅 | Novel environment-friendly production process of 1-naphthol-4-sulfonic acid |
| CN105017098A (en) * | 2015-07-17 | 2015-11-04 | 大连奇凯医药科技有限公司 | Preparation technology of alkyloxybenzsulfamide and its derivatives |
Non-Patent Citations (1)
| Title |
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| Synthesis and D2 Dopaminergic Activity of Pyrrolidinium,Tetrahydrothiophenium, and Tetrahydrothiophene Analogues of Sulpiride;Marc W. Harrold等;《J.Med.Chem.》;19891231;第32卷;874-880 * |
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