CN1982267A - Method for converting carbon tetrachloride into methane chloride - Google Patents
Method for converting carbon tetrachloride into methane chloride Download PDFInfo
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- CN1982267A CN1982267A CN 200510045578 CN200510045578A CN1982267A CN 1982267 A CN1982267 A CN 1982267A CN 200510045578 CN200510045578 CN 200510045578 CN 200510045578 A CN200510045578 A CN 200510045578A CN 1982267 A CN1982267 A CN 1982267A
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- Prior art keywords
- carbon tetrachloride
- tetracol phenixin
- reaction
- chloride
- methyl alcohol
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Abstract
Method for converting carbon tetrachloride into methane chloride is carried out by gas-phase reacting for carbon tetrachloride, methanol and hydrogen chloride in proportion of 1:2-8:0.5-4 under the existence of catalyst to obtain final product. Gamma-Al203 or gamma-Al203 with immersed zinc chloride is used as catalyst. It has better conversion rate and selectivity and long catalyst life.
Description
Technical field
The present invention relates to the method for converting carbon tetrachloride into methane chloride.
Background technology
Tetracol phenixin is the main by product of methane chloride device, and it can consume the ozonosphere in the atmosphere stratosphere strongly.China has added Montreal Protocol on Substances that Deplete the Ozone Layer in 1991, to progressively cut down and the production and the use of Ozone Depleting Substances such as superseded tetracol phenixin, therefore develop tetracol phenixin and transform and become a ten minutes urgent subject with treatment technology.
Monochloro methane is mainly used in and produces organosilyl intermediate methyl silicon, the solvent as the isoprene-isobutylene rubber polymerizing catalyst, the extraction agent of heat-sensitive substance, production tetramethyl plumbane, methylcellulose gum and weedkiller etc. except that methylene dichloride and chloroform are produced in further chlorination.
The reaction of tetracol phenixin and methyl alcohol can be carried out in liquid phase, also can carry out in gas phase.The patent No. is that 95108577.8 Chinese patent discloses a kind of alcoholysis of carbon tetrachloride method.This method is that tetracol phenixin and methyl alcohol are fed in the solder(ing)acid with the preparation monochloro methane, in embodiment, and the transformation efficiency of its tetracol phenixin about 77%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of converting carbon tetrachloride into methane chloride, and tetracol phenixin has higher conversion, the selectivity height of monochloro methane, catalyzer long service life.
The method of converting carbon tetrachloride into methane chloride of the present invention is characterized in that it being by tetracol phenixin and methyl alcohol and hydrogenchloride gas-phase reaction generation monochloro methane under catalyzer.
The reaction equation that the present invention relates to is:
CH
3OH+HCl→CH
3Cl+H
2O
CCl
4+2H
2O→4HCl+CO
2
The total reaction equation is: CCl
4+ 4CH
3OH → 4CH
3Cl+2H
2O+CO
2
Catalyst system therefor of the present invention is γ-Al
2O
3Or the γ-Al of dipping zinc chloride
2O
3Can be only with γ-Al
2O
3Make catalyzer, also can be at γ-Al
2O
3Last dipping accounts for 1%～40% zinc chloride of catalyst weight, preferably floods the zinc chloride of 10%～30% (weight ratio).The present invention finds, with γ-Al
2O
3Make catalyzer and can reach higher carbon tetrachloride conversion and higher monochloro methane selectivity.γ-Al with the dipping zinc chloride
2O
3Make catalyzer and can reach higher carbon tetrachloride conversion.
Tetracol phenixin, methyl alcohol and hydrogenchloride pass through catalyzer with the gas phase successive by a certain percentage, air speed is 1～60s, its ratio is a tetracol phenixin: methyl alcohol: hydrogenchloride=1: 2～8: 0.5～4 (mol ratio), preferred ratio is a tetracol phenixin: methyl alcohol: hydrogenchloride=1: 3～7: 0.7～3 (mol ratio).
The present invention finds that feeding a certain amount of hydrogenchloride is favourable to converting carbon tetrachloride into methane chloride, can improve the selectivity of monochloro methane and prolong catalyst life.The selectivity of monochloro methane is more than 99%, and life of catalyst was through the active decline about 10% of life experiment in 1000 hours.
Converting carbon tetrachloride into methane chloride carries out at a certain temperature, and its temperature of reaction is 150 ℃～300 ℃, and preferred temperature of reaction is 180 ℃～280 ℃, and reaction pressure is 0～0.5Mpa.
Advantage of the present invention:
Tetracol phenixin has higher conversion, the selectivity height of monochloro methane, catalyzer long service life.
Embodiment
Describe the present invention in detail by following examples, not delimit the scope of the invention.
Embodiment 1
In tubular reactor, adopt γ-Al
2O
3Catalyzer, catalyzer are cylindric, the about 200m of its specific surface area
2/ g.Tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 4: 0.5,200 ℃ of temperature of reaction, and during reaction pressure 0.1Mpa, assay products, can calculate carbon tetrachloride conversion is 87%, the monochloro methane selectivity is 99%.
Embodiment 2
Identical with embodiment 1, just tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are become 1: 5: 1,220 ℃ of temperature of reaction, assay products, can calculate carbon tetrachloride conversion is 90%, the monochloro methane selectivity is 99%.
Embodiment 3
In tubular reactor, adopt the γ-Al of dipping 15% zinc chloride
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 7: 3,250 ℃ of temperature of reaction, and during reaction pressure 0.2Mpa, assay products, can calculate carbon tetrachloride conversion is 95%, the monochloro methane selectivity is 99%.
Embodiment 4
In tubular reactor, adopt the γ-Al of dipping 25% zinc chloride
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 3: 0.5,260 ℃ of temperature of reaction, and during reaction pressure 0.3Mpa, assay products, can calculate carbon tetrachloride conversion is 88%, the monochloro methane selectivity is 99%.
Embodiment 5
In tubular reactor, adopt γ-Al
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 6: 2,180 ℃ of temperature of reaction, and during reaction pressure 0.3Mpa, assay products, can calculate carbon tetrachloride conversion is 91%, the monochloro methane selectivity is 99%.
Embodiment 6
In tubular reactor, adopt the γ-Al of dipping 8% zinc chloride
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 2: 1,240 ℃ of temperature of reaction, and during reaction pressure 0.5Mpa, assay products, can calculate carbon tetrachloride conversion is 85%, the monochloro methane selectivity is 98%.
Embodiment 7
In tubular reactor, adopt the γ-Al of dipping 35% zinc chloride
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 8: 4,270 ℃ of temperature of reaction, and during reaction pressure 0.3Mpa, assay products, can calculate carbon tetrachloride conversion is 94%, the monochloro methane selectivity is 99%.
Embodiment 8
In tubular reactor, adopt γ-Al
2O
3Make catalyzer, tetracol phenixin, methyl alcohol and hydrogenchloride raw materials components mole ratio are 1: 5.5: 1.5,290 ℃ of temperature of reaction, and during reaction pressure 0.25Mpa, assay products, can calculate carbon tetrachloride conversion is 90%, the monochloro methane selectivity is 99%.
Claims (5)
1, a kind of method of converting carbon tetrachloride into methane chloride is characterized in that it being by tetracol phenixin and methyl alcohol and hydrogenchloride gas-phase reaction generation monochloro methane under catalyzer.
2, method according to claim 1 is characterized in that described catalyzer is γ-Al
2O
3Or the γ-Al of dipping zinc chloride
2O
3, the pickup of zinc chloride is 1～40% of a catalyst weight.
3, method according to claim 1 is characterized in that described reaction raw materials raw materials components mole ratio is: tetracol phenixin: methyl alcohol: hydrogenchloride=1: 2～8: 0.5～4.
4, method according to claim 1 is characterized in that temperature of reaction is 150 ℃～300 ℃.
5, method according to claim 1 is characterized in that reaction pressure is 0～0.5Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510045578 CN1982267A (en) | 2005-12-13 | 2005-12-13 | Method for converting carbon tetrachloride into methane chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510045578 CN1982267A (en) | 2005-12-13 | 2005-12-13 | Method for converting carbon tetrachloride into methane chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1982267A true CN1982267A (en) | 2007-06-20 |
Family
ID=38165162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510045578 Pending CN1982267A (en) | 2005-12-13 | 2005-12-13 | Method for converting carbon tetrachloride into methane chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1982267A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921166A (en) * | 2010-08-27 | 2010-12-22 | 山东东岳氟硅材料有限公司 | Liquid phase production technology for preparing methane chloride with carbon tetrachloride |
| CN107213910A (en) * | 2017-05-15 | 2017-09-29 | 石河子大学 | A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride |
-
2005
- 2005-12-13 CN CN 200510045578 patent/CN1982267A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921166A (en) * | 2010-08-27 | 2010-12-22 | 山东东岳氟硅材料有限公司 | Liquid phase production technology for preparing methane chloride with carbon tetrachloride |
| CN101921166B (en) * | 2010-08-27 | 2013-06-12 | 山东东岳氟硅材料有限公司 | Liquid phase production technology for preparing methane chloride with carbon tetrachloride |
| CN107213910A (en) * | 2017-05-15 | 2017-09-29 | 石河子大学 | A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride |
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