CN1515528A - Pressure synthesis and refining process of methane chloride - Google Patents
Pressure synthesis and refining process of methane chloride Download PDFInfo
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- CN1515528A CN1515528A CNA031000363A CN03100036A CN1515528A CN 1515528 A CN1515528 A CN 1515528A CN A031000363 A CNA031000363 A CN A031000363A CN 03100036 A CN03100036 A CN 03100036A CN 1515528 A CN1515528 A CN 1515528A
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Abstract
The present invention relates to a new process for producing methane chloride by using liquid-phase catalytic method and pressurization process. The hydrogen chloride and methyl alcohol are mixed according to a certain ratio, then placed in a tank reactor with catalyst, and under the condition of a certain temp. and pressure the invented methane chloride can be synthesized. It adopts acid/water washing and alkali-washing processes to remove unreacted methyl alcohol and hydrogen chloride, and adopts concentrated sulfuric acid washing process to remove residual water content and reaction by-product dimethyl ether, then the purified and dried methane chloride gas is undergone the processes of compression and condensation so as to obtain high-purity liquid methane chloride product.
Description
Technical field:
The present invention is for producing the advanced preparation method of methyl chloride.
Background technology:
At present, methyl chloride has 3 kinds of industrial processes, i.e. by-product absorption method, methane chlorination method, methyl alcohol hydrochlorinate method.
The by-product absorption method be the methyl chloride that will produce in the pesticide producing process, hydrogenchloride mixed tail gas through lyophilization, again through vitriol oil drying, in the solid caustic soda and deacidification, compressed then, condensation liquefaction gets the product methyl chloride.But the by-product absorption method is because of being limited by agricultural chemicals Trichlorphon production and selling, and the methyl chloride turnout is restricted, and product purity does not satisfy the requirement of synthesizing methyl-chloro-silane.
The methane chlorination method is that methane and chlorine are carried out chlorination under 400 ℃ of high temperature, and chlorizate absorbs through water and removes de-chlorine hydride, and the unreacted methane aftercut of compressed again, condensation separation goes out methyl chloride and polychloride.The methane chlorination method is suitable for producing polychloride, and per unit area yield monochloro methane person is generally without this method.
The methyl alcohol chlorination process is after hydrogenchloride and methyl alcohol are proportioned, to carry out building-up reactions under certain condition and generate thick product methyl chloride, obtains the liquid methyl chloride through purification, drying, compression, condensation again.The present invention has raw material and is easy to get, level of automation height, yield advantages of higher.
Summary of the invention:
The novel process that the present invention produces monochloro methane for the liquid catalytic pressurization.Methyl alcohol and hydrogenchloride through vaporization enter in the reactor that liquor zinci chloridi is housed by a certain percentage, and reaction under certain condition generates methyl chloride.Methyl chloride etc. and unreacted completely hydrogenchloride, methyl alcohol together through the condenser cooling condensation, enter vapour liquid separator after water and the methanol condensed, methyl chloride, dme and unreacted hydrogen chloride, methyl alcohol enter sour water together and wash at the bottom of the Tata, sour water is washed column overhead and is added quantitative water, most of hydrogenchloride, methyl alcohol are removed, the acid that produces enters dilute acid bath by the tower still, and methyl chloride and dme and a small amount of hydrogenchloride are washed at the bottom of column overhead enters the alkali cleaning Tata by sour water.The soda-wash tower cat head adds the caustic soda washings, and the hydrogenchloride in the methyl chloride is removed, and the alkali lye after the washing enters the salkali waste groove by the tower still.Methyl chloride and dme and residual water are gone into by the soda-wash tower jacking at the bottom of the sulfuric acid tower tower, adopt the placed in-line sulfuric acid countercurrent flow of multitower to carry out drying.Through a plurality of sulfuric acid towers the water of remnants and the dme in the byproduct of reaction are removed, the methyl chloride gas behind purge drying enters compressor by the drying tower cat head, and compressed, condensation obtains highly purified liquid methyl chloride product.
The alkyd that contains of dilute acid bath is squeezed into dealcoholize column by pump, after dealcoholize column separates, obtain 15-20% hydrochloric acid at the bottom of the tower, the methyl alcohol that cat head obtains and a small amount of hydrogenchloride and water, its methanol content is controlled at 50-80% (wt), after condenser condenses, phlegma enters return tank by cat head, and a part enters the methyl chloride reactor.
Temperature of reaction kettle of the present invention adopts extracorporeal circulation control, and promptly reaction solution shifts out or additional heat through the still external heat exchanger by recycle pump, avoids reactor to produce quenching, shock heating phenomenon, prolongs the work-ing life of reactor.
The present invention has following characteristics:
1, the synthetic pressurization technology that adopts of methane, and adopt extracorporeal circulation technology, the heat exchange of realization response avoids reactor to produce quenching, shock heating phenomenon, prolongs the work-ing life of reactor.
2, separate feeding manner with gas-phase methanol and hydrogenchloride.
3, methyl chloride refining system acid water wash column adopts the circulation absorption technique, and pickling tower and water wash column are merged into a tower, by the extracorporeal circulation and the adjusting amount of makeup water of tower bottoms, the assimilated efficiency of control tower and concentration of hydrochloric acid.
4, the soda-wash tower of methyl chloride refining system is by the external assimilated efficiency and the concentration of lye that self circulates and regulate alkali number (adding 10% caustic soda soln) control tower of tower bottoms.
5, the sulfuric acid drying process of methane refining system adopts the placed in-line sulfuric acid countercurrent flow of multitower, simplifies technology, and energy efficient has improved the yield of methyl chloride.
6, dilute hydrochloric acid dealcoholysis and dilute hydrochloric acid are put forward dense technology, have realized the recycling of methyl alcohol and chlorination chlorine.
Embodiment
Enter by a certain percentage in the reactor that liquor zinci chloridi is housed through the methyl alcohol of vaporization and the hydrogenchloride that takes off suction from hydrochloric acid, at 160 ℃, 0.2MPa reaction down generates methyl chloride.Methyl chloride etc. and unreacted hydrogen chloride, methyl alcohol through the condenser condenses cooling, enter vapour liquid separator after portion water and the methanol condensed together, are back to by separator and come conditioned reaction still temperature in the reactor.Reaction generation methyl chloride etc. and unreacted hydrogen chloride, methyl alcohol enter at the bottom of the sour water Tata together, the sour water column overhead adds quantitative water, most of hydrogenchloride, methyl alcohol are removed, the acid that produces enters dilute acid bath by the tower still, and methyl chloride, dme and a small amount of hydrogenchloride are washed at the bottom of column overhead enters the alkali cleaning Tata by sour water.The soda-wash tower cat head adds 10% caustic soda washings, and the hydrogenchloride in the methyl chloride is removed, and the alkali lye after the washing enters the salkali waste groove by the tower still.Methyl chloride and dme and residual water are gone into by the soda-wash tower jacking at the bottom of the dry I Tata of sulfuric acid, again at the bottom of the I column overhead enters the dry II Tata of sulfuric acid, enter the dry III Tata of sulfuric acid by the II column overhead at the bottom of.Dry three towers all adopt self-circulation, and the vitriol oil is added by the dry III tower of sulfuric acid, and overflow is to the II tower again, by the II tower again overflow adopt three tower cascade connected sulfuric acid countercurrent flow to carry out drying to the I tower.Through three sulfuric acid towers the water of remnants and the dme in the reaction by-product are removed, the methyl chloride gas behind purge drying enters compressor by dry III column overhead, and compressed, condensation gets highly purified liquid methyl chloride product.The tower top temperature and tower self internal circulating load of control sour water tower and soda-wash tower.The temperature control of the dry I column overhead of sulfuric acid is at 22 ℃, and the sulfuric acid internal circulating load is 25m
3/ h, dry II column overhead temperature is controlled at 22 ℃, sulfuric acid internal circulating load 25m
3/ h, 25 ℃ of internal circulating load 25m of dry III cat head temperature
3/ h, sulfuric acid concentration is greater than 84% in the dry I tower of sulfuric acid, and dry II tower sulfuric acid concentration is greater than 91%, and sulfuric acid concentration is greater than 93% in the dry III tower.
The alkyd that contains of dilute acid bath is squeezed into dealcoholize column by pump, after dealcoholize column separates, obtain 15% hydrochloric acid at the bottom of the tower, the methyl alcohol that cat head obtains and a small amount of hydrogenchloride and water, its methanol content is controlled at 60% (wt), after condenser condenses, phlegma enters return tank by cat head, and a part enters the methyl chloride reactor.
Claims (8)
1, methyl chloride synthesis technology of the present invention is the novel process that monochloro methane is produced in the liquid catalytic pressurization, and methyl alcohol and hydrogenchloride through vaporizing enter in the reactor that liquor zinci chloridi is housed by a certain percentage, and reaction generates methyl chloride.The present invention avoids reactor to produce quenching, shock heating phenomenon by the extracorporeal circulation of material, prolongs the work-ing life of reactor.
2, temperature of reaction kettle is 140-170 ℃.
3, reactor pressure is 0.05-0.25Mpa.
4, the methyl chloride process for refining is that the methyl chloride that contains impurity such as methyl alcohol, hydrogenchloride, water is removed impurity through acid rinsing tower, soda-wash tower, sulfuric acid tower.
5, soda-wash tower caustic soda concentration is 5～15%.
6, by the placed in-line sulfuric acid reflux type of multitower, in sulfuric acid tower, water in the methyl chloride and dme are removed.
7, the temperature control of sulfuric acid tower cat head is at 20-40 ℃, and the sulfuric acid internal circulating load is 15-40m
3/ h.
8, dilute hydrochloric acid dealcoholysis technology is that the alkyd that contains that sour water wash column comes is squeezed into dealcoholize column by pump, after dealcoholize column separates, obtain 15-20% hydrochloric acid at the bottom of the tower, the methyl alcohol that cat head obtains and a small amount of hydrogenchloride and water, its methanol content is controlled at 50-80% (wt), after condenser condenses, phlegma enters return tank by cat head, and a part enters the methyl chloride reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03100036 CN1212298C (en) | 2003-01-07 | 2003-01-07 | Pressure synthesis and refining process of methane chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03100036 CN1212298C (en) | 2003-01-07 | 2003-01-07 | Pressure synthesis and refining process of methane chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1515528A true CN1515528A (en) | 2004-07-28 |
| CN1212298C CN1212298C (en) | 2005-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03100036 Expired - Fee Related CN1212298C (en) | 2003-01-07 | 2003-01-07 | Pressure synthesis and refining process of methane chloride |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970080A (en) * | 2008-03-20 | 2011-02-09 | 弗洛技术控股有限公司 | Gas treatment apparatus-water flooded screw compressor |
| CN101503336B (en) * | 2009-03-06 | 2013-03-13 | 刘世刚 | Improved methane chloride production process |
| CN103011093A (en) * | 2012-12-25 | 2013-04-03 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Device and method for removing siloxane in dilute sulfuric acid |
| CN103435438A (en) * | 2013-08-08 | 2013-12-11 | 顾志祥 | Production method of methane chloride |
| US8859830B2 (en) | 2009-03-05 | 2014-10-14 | Dow Global Technologies Inc. | Methods and assemblies for liquid-phase reactions |
| CN111018660A (en) * | 2019-03-11 | 2020-04-17 | 北京诺维新材科技有限公司 | Separation method of chloromethane material |
| CN113582811A (en) * | 2020-04-30 | 2021-11-02 | 蓝星（北京）技术中心有限公司 | Deacidification method of methane chloride |
| CN113828001A (en) * | 2021-10-29 | 2021-12-24 | 新疆晶硕新材料有限公司 | Separation system and separation method of chloromethane |
-
2003
- 2003-01-07 CN CN 03100036 patent/CN1212298C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970080A (en) * | 2008-03-20 | 2011-02-09 | 弗洛技术控股有限公司 | Gas treatment apparatus-water flooded screw compressor |
| US8859830B2 (en) | 2009-03-05 | 2014-10-14 | Dow Global Technologies Inc. | Methods and assemblies for liquid-phase reactions |
| CN101503336B (en) * | 2009-03-06 | 2013-03-13 | 刘世刚 | Improved methane chloride production process |
| CN103011093A (en) * | 2012-12-25 | 2013-04-03 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Device and method for removing siloxane in dilute sulfuric acid |
| CN103011093B (en) * | 2012-12-25 | 2014-05-28 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Device and method for removing siloxane in dilute sulfuric acid |
| CN103435438A (en) * | 2013-08-08 | 2013-12-11 | 顾志祥 | Production method of methane chloride |
| CN103435438B (en) * | 2013-08-08 | 2015-11-25 | 顾志祥 | The production method of monochloro methane |
| CN111018660A (en) * | 2019-03-11 | 2020-04-17 | 北京诺维新材科技有限公司 | Separation method of chloromethane material |
| CN113582811A (en) * | 2020-04-30 | 2021-11-02 | 蓝星（北京）技术中心有限公司 | Deacidification method of methane chloride |
| CN113828001A (en) * | 2021-10-29 | 2021-12-24 | 新疆晶硕新材料有限公司 | Separation system and separation method of chloromethane |
| CN113828001B (en) * | 2021-10-29 | 2022-10-11 | 新疆晶硕新材料有限公司 | Separation system and separation method of chloromethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1212298C (en) | 2005-07-27 |
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