CN102153439A - Process for producing high-purity methane chloride - Google Patents
Process for producing high-purity methane chloride Download PDFInfo
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- CN102153439A CN102153439A CN200810238071XA CN200810238071A CN102153439A CN 102153439 A CN102153439 A CN 102153439A CN 200810238071X A CN200810238071X A CN 200810238071XA CN 200810238071 A CN200810238071 A CN 200810238071A CN 102153439 A CN102153439 A CN 102153439A
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Abstract
The invention provides a process for producing high-purity methane chloride. The process comprises the following steps of: introducing vaporized and overheated methanol and hydrogen chloride a reactor containing an alumina catalyst and reacting in the reactor to generate a mixture of methane chloride, methane, chloroethane and dichloromethane; introducing the generated mixture to a chilling device, carrying out chilling separation and then introducing into an acid-washing tower, an alkaline washing tower and a sulfuric acid drying system, compressing to prepare coarse methane chloride; leading the coarse methane chloride into a treating column and separating out heavy components from the bottom of the treating column; evaporating light-component methane and methane chloride to the top of the treating column together; then performing water cooling and deep freezing so that the methane chloride is liquefied, completely discharging the methane which is not liquefied into an exhaust washing tower by a deep freezer so as to separate methane chloride from methane and finally obtain high-purity methane chloride. In the invention, a single-tower rectification manner is adopted, therefore, equipment investment is not increased greatly, but also the content of methane chloride is increased to be higher than 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, 25-45 ℃ of tower top temperatures, and 55-80 ℃ of column bottom temperatures, 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, 3-5% the alkali that goes out 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, 25-45 ℃ of tower top temperatures, and 55-80 ℃ of column bottom temperatures, 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%.
Claims (6)
1. the production method of a high-purity 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.
2. the production method of high-purity 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 high-purity 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 high-purity 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.
5. the production method of high-purity monochloro methane as claimed in claim 1 is characterized in that, 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; 21～24% the hydrochloric acid that goes out the pickling tower is produced 31% hydrochloric acid, and the alkali that goes out the 3-5% of soda-wash tower enters in the exhaust washing system and sour gas.
6. the production method of high-purity monochloro methane as claimed in claim 1, it is characterized in that, thick monochloro methane enters the monochloro methane treating tower in the step 3), tower top pressure is 0.45-0.62Mpa, tower bottom pressure is 0.5-0.67Mpa, 25-45 ℃ of tower top temperatures, 55-80 ℃ of column bottom temperatures, reflux ratio is 3～8.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838629A (en) * | 2012-09-29 | 2012-12-26 | 山东金岭化学有限公司 | Novel process for synthesizing methyl chlorosilane by methane chloride byproduct chloromethane |
| CN103626624A (en) * | 2012-08-29 | 2014-03-12 | 曹汉平 | Method for preventing corrosion on methane chloride chlorination device |
| CN105016965A (en) * | 2015-07-06 | 2015-11-04 | 淮阴师范学院 | Separation of chloromethane and chloroethane mixture by throttling expansion method |
| CN109081767A (en) * | 2018-09-30 | 2018-12-25 | 南京佳华工程技术有限公司 | A kind of the synthesis rectification technique and its equipment of monochloro methane |
| CN109438169A (en) * | 2018-12-10 | 2019-03-08 | 安徽金禾实业股份有限公司 | The processing method of waste hydrochloric acid in a kind of production of Sucralose |
| CN111499490A (en) * | 2020-04-27 | 2020-08-07 | 山东东岳氟硅材料有限公司 | Method for producing methane chloride by using byproduct fluorine-containing hydrogen chloride |
-
2008
- 2008-12-08 CN CN200810238071XA patent/CN102153439A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626624A (en) * | 2012-08-29 | 2014-03-12 | 曹汉平 | Method for preventing corrosion on methane chloride chlorination device |
| CN102838629A (en) * | 2012-09-29 | 2012-12-26 | 山东金岭化学有限公司 | Novel process for synthesizing methyl chlorosilane by methane chloride byproduct chloromethane |
| CN102838629B (en) * | 2012-09-29 | 2015-02-18 | 山东金岭化学有限公司 | Novel process for synthesizing methyl chlorosilane by methane chloride byproduct chloromethane |
| CN105016965A (en) * | 2015-07-06 | 2015-11-04 | 淮阴师范学院 | Separation of chloromethane and chloroethane mixture by throttling expansion method |
| CN109081767A (en) * | 2018-09-30 | 2018-12-25 | 南京佳华工程技术有限公司 | A kind of the synthesis rectification technique and its equipment of monochloro methane |
| CN109081767B (en) * | 2018-09-30 | 2021-04-06 | 南京佳华工程技术有限公司 | Synthetic rectification process method and equipment for methane chloride |
| CN109438169A (en) * | 2018-12-10 | 2019-03-08 | 安徽金禾实业股份有限公司 | The processing method of waste hydrochloric acid in a kind of production of Sucralose |
| CN111499490A (en) * | 2020-04-27 | 2020-08-07 | 山东东岳氟硅材料有限公司 | Method for producing methane chloride by using byproduct fluorine-containing hydrogen chloride |
| 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 |
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Open date: 20110817 |