CN100579945C - Production technique of high-purity methane chloride - Google Patents
Production technique of high-purity methane chloride Download PDFInfo
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- CN100579945C CN100579945C CN200710113228A CN200710113228A CN100579945C CN 100579945 C CN100579945 C CN 100579945C CN 200710113228 A CN200710113228 A CN 200710113228A CN 200710113228 A CN200710113228 A CN 200710113228A CN 100579945 C CN100579945 C CN 100579945C
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Abstract
The process of producing high purity methane chloride includes the following steps: the reaction of vaporized and overheated methane and hydrogen chloride inside a reactor with alumina catalyst to produce mixture of methane chloride, methane, ethane chloride and methane dichloride; chilling separation of the mixture in a chiller, and treating in an acid pickling tower, a alkaline washing tower, a sulfuric acid drying system and a compression unit to obtain coarse methane chloride product; separating in a methane chloride refining tower to eliminate heavy component in the bottom and light components include methane and methane chloride in the top; and water cooling and refrigerating the light components to liquefy methane chloride as the high purity product while discharging un-liquefied methane. The process with single tower rectification has high methane chloride purity over 99.98 %.
Description
Technical field
The present invention relates to the production technique of methane chloride, particularly a kind of production method of high purity monochloro methane.
Background technology
Along with the development of organosilicon industry and continually developing of monochloro methane derived product, demand to the monochloro methane commodity amount is increasing, but present stage, most methane chloride production device was that the difficult quality of monochloro methane reaches market demands as corollary apparatus production.Present stage, synthetic monochloro methane all adopted gas and solid phase catalytic and liquid catalytic, in the gas and solid phase catalytic production technique, two kinds of production methods was arranged:
A kind of be thick monochloro methane through catalyzed reaction after Quench, compression makes monochloro methane after washing, alkali cleaning, sulfuric acid drying successively.CN1686981 discloses a kind of preparation method of methane chloride.It is a raw material with methyl alcohol and hydrogenchloride, active catalyst exists down, at 260-320 ℃, 0.2-0.6MpaG under the condition, gas-phase reaction generates monochloro methane and water, go out the reactor high temperature reaction gas after the dilute hydrochloric acid Quench, separate the back moisture through condenser condenses (phlegma is that dilute hydrochloric acid is used for the reaction gas Quench), sulfuric acid drying, compression condensation make monochloro methane.CN1515528 discloses the technology that monochloro methane is produced in the liquid catalytic pressurization, after hydrogenchloride and methyl alcohol proportioned, in the tank reactor of catalyzer is housed, synthetic monochloro methane under certain temperature and pressure, and adopt acid/washing, alkali cleaning to remove unreacted methanol and hydrogenchloride, and adopt vitriol oil washing to remove the dme of remaining moisture content and reaction by-product; Obtain highly purified liquid monochloro methane product through purification, dried methyl chloride gas by compression, condensation.This production method waste water, salkali waste quantity discharged are big, pollute highly, and the monochloro methane content of production is low, generally between 97%--99%, can't satisfy the high-end market needs.
Another kind is thick monochloro methane without washing, alkali cleaning, and directly the dry compression of sulfuric acid makes monochloro methane, and the mode by two tower rectifying makes the higher monochloro methane of purity then.
A kind of production method of high-purity monochloro methane is disclosed at CN1686983A.With methyl alcohol and hydrogenchloride is raw material, active catalyst exists down, at 280-320 ℃, 0.2-0.6MpaG under the condition, gas-phase reaction generates monochloro methane and water, go out the reactor high temperature reaction gas after the dilute hydrochloric acid Quench, separate the back moisture through condenser condenses (phlegma is that dilute hydrochloric acid is used for the reaction gas Quench), sulfuric acid drying, compression condensation make the thick product of monochloro methane.Remove light component in the monochloro methane coarse fodder by first rectifying tower, remove heavy component by second rectifying tower again.Though this method has improved monochloro methane content, but owing to do not have caustic wash process in the production process of the thick product of monochloro methane, cause in the thick product of monochloro methane acidity higher, when rectifying, the rectifying tower material is required than higher, and its disclosed rectifying mode is to remove light constituent in the monochloro methane coarse fodder by first rectifying tower, removes heavy constituent by second rectifying tower again.The mode of two tower rectifying has increased facility investment, has improved working cost.
Summary of the invention
For overcoming the deficiencies in the prior art, for solving these two kinds quality and the environmental issues in the synthetic monochloro methane process, reduce the production cost of monochloro methane, the invention provides a kind of production method of high-purity monochloro methane.
The invention provides a kind of production method of high-purity monochloro methane, comprise the following steps:
1) methyl alcohol and hydrogenchloride enter the reactor that aluminium oxide catalyst is housed through vaporizing after overheated, generate the mixture of monochloro methane, methane, monochloroethane, methylene dichloride at the reactor internal reaction; The mol ratio of hydrogenchloride and methyl alcohol is 1.1-1.2: 1.
2) mixture of step 1) generation enters chiller, enters the pickling tower after Quench is separated, soda-wash tower, and the sulfuric acid dehumidification system makes thick monochloro methane after the compression;
3) thick monochloro methane enters the monochloro methane treating tower, by isolating heavy constituent at the bottom of the tower; Light constituent methane and monochloro methane are evaporated to cat head together, and after water-cooled and deep cooling, monochloro methane liquefaction, and Ye Hua methane then is not emptied to vent scrubber by deep freezer, thus separating of realization monochloro methane and methane obtains highly purified monochloro methane.
Described reorganization is divided into monochloroethane, methylene dichloride.
In the thick product of monochloro methane, contain light constituent methane, heavy constituent monochloroethane, methylene dichloride etc.Heavy constituent proportion and temperature of reaction and reaction pressure have substantial connection, and the suitable reduction of temperature of reaction and reaction pressure can reduce the growing amount of heavy constituent.Preferably, temperature of reaction is 200-300 ℃ in the step 1) reactor, and pressure is 0.15-0.4MpaG, and temperature of reaction is 230-300 ℃ in the preferred reactor, and pressure is 0.15-0.3MpaG.
Aluminium oxide catalyst is housed in the reactor, and catalyzer can use catalyzer well known in the art, also can use the described catalyzer of CN1515528.The present invention does not do special qualification to the production method of thick monochloro methane, can use any prior art disclosed method to produce thick monochloro methane, makes with extra care according to step 3) then.
Compare with monochloro methane, methane is difficult for liquefaction, just is being based on this, has invented the single tower distillation technology.In same rectifying tower, by isolating heavy constituent at the bottom of the tower; Light constituent methane and monochloro methane are evaporated to cat head together, and after water-cooled and deep cooling, monochloro methane liquefaction, and Ye Hua methane then is not emptied to vent scrubber by deep freezer, thus separating of realization monochloro methane and methane obtains highly purified monochloro methane.
Preferably, step 2) in mixture in chiller after the dilute hydrochloric acid Quench temperature be reduced to 50--100 ℃.Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.
Preferably, in the pickling tower with unreacted hydrogen chloride in the dilute hydrochloric acid absorption reaction gas after the Quench, in soda-wash tower with unabsorbed hydrogenchloride in the 10% sodium hydroxide neutralization reaction gas.The hydrochloric acid that goes out pickling tower about 22% is produced 31% hydrochloric acid, and the alkali that goes out the about 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.
Preferably, thick monochloro methane enters the monochloro methane treating tower in the step 3), and tower top pressure is 0.45-0.62Mpa, and tower bottom pressure is 0.5-0.67Mpa, and tower top temperature 25-45 ℃, column bottom temperature 55-80 ℃, reflux ratio is 3～8.Cat head removes light constituent through cooling, deep cooling, removes heavy constituent at the bottom of the tower, thereby obtains surpassing high-purity monochloro methane commodity of 99.98%.
Advantage of the present invention is: the present invention includes pickling, alkali cleaning, sulfuric acid drying, go out 22% hydrochloric acid of pickling tower, the alkali that goes out the 3-5% of soda-wash tower has all been done to deal carefully with environmentally safe.The present invention has adopted the mode of single tower distillation, realizes separating of monochloro methane and methane in same rectifying tower, obtains highly purified monochloro methane.Neither roll up facility investment, improved the content of monochloro methane again, make it greater than 99.98%.
Embodiment
Technical scheme of the present invention is: methyl alcohol and hydrogenchloride are in the presence of activated alumina catalyst, and at 200-300 ℃, under the 0.15-0.4MpaG condition, gas-phase reaction generates monochloro methane and water.Gas phase resultant temperature after the dilute hydrochloric acid Quench is reduced to 50--100 ℃.Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.In the pickling tower with unreacted hydrogen chloride in the dilute hydrochloric acid absorption reaction gas after the Quench, in soda-wash tower with unabsorbed hydrogenchloride in the 10% sodium hydroxide neutralization reaction gas.The hydrochloric acid that goes out pickling tower about 22% is produced 31% hydrochloric acid, and the alkali that goes out the about 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.Thick monochloro methane enters the monochloro methane treating tower, and tower top pressure is 0.45-0.62Mpa, and tower bottom pressure is 0.5-0.67Mpa, and tower top temperature 25-45 ℃, column bottom temperature 55-80 ℃, reflux ratio is 3～8.Cat head removes light constituent through cooling, deep cooling, removes heavy constituent at the bottom of the tower, thereby obtains surpassing high-purity monochloro methane commodity of 99.98%.
By the following examples the present invention is further specified.The present invention is not limited to this
Embodiment 1
Methyl alcohol and hydrogenchloride are in the presence of activated alumina catalyst, and at 210 ℃, under the 0.18MpaG condition, gas-phase reaction generates monochloro methane and water.Gas phase resultant temperature after the dilute hydrochloric acid Quench is reduced to 50 ℃.Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.In the pickling tower with unreacted hydrogen chloride in the dilute hydrochloric acid absorption reaction gas after the Quench, in soda-wash tower with unabsorbed hydrogenchloride in the 10% sodium hydroxide neutralization reaction gas.The hydrochloric acid that goes out pickling tower 22% is produced 31% hydrochloric acid, and the alkali that goes out the about 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.
43 ℃ of monochloro methane rectifying tower tower top temperatures, tower top pressure 0.64Mpa, 78 ℃ of column bottom temperatures, tower bottom pressure 0.66Mpa, reflux ratio is 6, rectifying cooling back sampling analysis monochloro methane content is greater than 99.98%
Embodiment 2
Methyl alcohol and hydrogenchloride are in the presence of activated alumina catalyst, and at 300 ℃, under the 0.38MpaG condition, gas-phase reaction generates monochloro methane and water.Gas phase resultant temperature after the dilute hydrochloric acid Quench is reduced to 80 ℃.Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.In the pickling tower with unreacted hydrogen chloride in the dilute hydrochloric acid absorption reaction gas after the Quench, in soda-wash tower with unabsorbed hydrogenchloride in the 10% sodium hydroxide neutralization reaction gas.The hydrochloric acid that goes out pickling tower 22% is produced 31% hydrochloric acid, and the alkali that goes out the about 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.
35 ℃ of monochloro methane rectifying tower tower top temperatures, tower top pressure 0.62Mpa, 70 ℃ of column bottom temperatures, tower bottom pressure 0.64Mpa, reflux ratio is 5, rectifying cooling back sampling analysis monochloro methane content is greater than 99.98%
Embodiment 3
Methyl alcohol and hydrogenchloride are in the presence of activated alumina catalyst, and at 260 ℃, under the 0.30MpaG condition, gas-phase reaction generates monochloro methane and water.Gas phase resultant temperature after the dilute hydrochloric acid Quench is reduced to 100 ℃.Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.In the pickling tower with unreacted hydrogen chloride in the dilute hydrochloric acid absorption reaction gas after the Quench, in soda-wash tower with unabsorbed hydrogenchloride in the 10% sodium hydroxide neutralization reaction gas.The hydrochloric acid that goes out pickling tower 23% is produced 31% hydrochloric acid, and the alkali that goes out the about 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.
30 ℃ of monochloro methane rectifying tower tower top temperatures, tower top pressure 0.52Mpa, 60 ℃ of column bottom temperatures, tower bottom pressure 0.54Mpa, reflux ratio is 4, rectifying cooling back sampling analysis monochloro methane content is greater than 99.98%.
Claims (4)
1. the production method of a monochloro methane comprises the following steps:
1) methyl alcohol and hydrogenchloride enter the reactor that aluminium oxide catalyst is housed through vaporizing after overheated, generate the mixture of monochloro methane, methane, monochloroethane, methylene dichloride at the reactor internal reaction; The mol ratio of hydrogenchloride and methyl alcohol is 1.1-1.2: 1;
2) mixture of step 1) generation enters chiller, enters the pickling tower after Quench is separated, soda-wash tower, and the sulfuric acid dehumidification system makes thick monochloro methane after the compression;
3) thick monochloro methane enters the monochloro methane treating tower, by isolating heavy constituent at the bottom of the tower; Light constituent methane and monochloro methane are evaporated to cat head together, and after water-cooled and deep cooling, monochloro methane liquefaction, and Ye Hua methane then is not emptied to vent scrubber by deep freezer, thus separating of realization monochloro methane and methane obtains highly purified monochloro methane;
Described reorganization is divided into monochloroethane, methylene dichloride;
Thick monochloro methane enters the monochloro methane treating tower in the step 3), and tower top pressure is 0.45～0.62Mpa, and tower bottom pressure is 0.5～0.67Mpa, 25～45 ℃ of tower top temperatures, and 55～80 ℃ of column bottom temperatures, reflux ratio is 3～8.
2. the production method of monochloro methane as claimed in claim 1 is characterized in that, temperature of reaction is 200～300 ℃ in the step 1) reactor, and pressure is 0.15-0.4MpaG.
3. the production method of monochloro methane as claimed in claim 2 is characterized in that, temperature of reaction is 230～300 ℃ in the reactor, and pressure is 0.15-0.3MpaG.
4. the production method of monochloro methane as claimed in claim 1 is characterized in that step 2) in mixture in chiller after the dilute hydrochloric acid Quench temperature be reduced to 50～100 ℃; Liquid phase after the Quench is 20% dilute hydrochloric acid, and gas phase is successively through the overpickling tower, and soda-wash tower and sulfuric acid tower, compression condensation make thick monochloro methane.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101633599B (en) * | 2008-07-23 | 2013-11-06 | 汉能科技有限公司 | Method for preparing methane chloride by dimethyl sulfate |
| CN101429093B (en) * | 2008-11-28 | 2011-11-09 | 北京石油化工设计院有限公司 | Energy-saving process for producing monochloro methane with liquid phase catalysis method |
| CN104311383B (en) * | 2014-10-15 | 2016-05-04 | 山东东岳氟硅材料有限公司 | A kind of method of the hydrogen chloride production monochloro methane that utilizes by-product in tetrachloro-ethylene production process |
| CN105859513A (en) * | 2016-05-23 | 2016-08-17 | 河南红东方化工股份有限公司 | Production method for chloromethane |
| KR102087960B1 (en) * | 2018-09-18 | 2020-03-12 | 한국화학연구원 | A process of preparing methyl chloride using multistage reaction |
| CN109368896A (en) * | 2018-10-25 | 2019-02-22 | 苏州浩波科技股份有限公司 | For recycling the impurity remove device of methylene chloride |
| CN109534302A (en) * | 2018-11-13 | 2019-03-29 | 乳源东阳光电化厂 | A kind of method and its application for removing dimethyl sulfate in sulfuric acid |
| CN111039745B (en) * | 2019-12-25 | 2022-09-06 | 山东东岳氟硅材料有限公司 | System and method for reducing waste alkali in methane chloride production process |
| CN111499490B (en) * | 2020-04-27 | 2023-04-28 | 山东东岳氟硅材料有限公司 | Method for producing chloromethane by using byproduct fluorine-containing hydrogen chloride |
| CN112299947B (en) * | 2020-11-02 | 2022-11-08 | 山东东岳氟硅材料有限公司 | Method for preparing methane chloride by using fluorine chemical byproduct hydrogen chloride |
| CN112573995A (en) * | 2020-12-11 | 2021-03-30 | 安徽金禾实业股份有限公司 | Method for recovering byproduct chloromethane in maltol production process |
| CN113860988B (en) * | 2021-11-01 | 2023-07-25 | 新疆晶硕新材料有限公司 | System and method for separating chloroethane from chloromethane and system for synthesizing chloromethane |
| CN115850017A (en) * | 2022-11-30 | 2023-03-28 | 江西蓝星星火有机硅有限公司 | Preparation method and system of efficient chloromethane |
| CN115784833A (en) * | 2023-02-02 | 2023-03-14 | 山东东岳氟硅材料有限公司 | Emission reduction method and device for byproduct hydrochloric acid in chloromethane production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4220609A (en) * | 1976-12-09 | 1980-09-02 | General Electric Company | Process for the recovery of alkyl chlorides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4220609A (en) * | 1976-12-09 | 1980-09-02 | General Electric Company | Process for the recovery of alkyl chlorides |
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