CN101015809A - Method for extending life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis - Google Patents
Method for extending life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis Download PDFInfo
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- CN101015809A CN101015809A CNA2006100423321A CN200610042332A CN101015809A CN 101015809 A CN101015809 A CN 101015809A CN A2006100423321 A CNA2006100423321 A CN A2006100423321A CN 200610042332 A CN200610042332 A CN 200610042332A CN 101015809 A CN101015809 A CN 101015809A
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- carbon tetrachloride
- oxygen
- chlorine
- catalyst
- hydrogen chloride
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for prolonging the service life of the catalyst used to alcoholysis of carbon tetrachloride to prepare chloromethane, wherein the material carbon tetrachloride is reacted with carbinol in catalyst condition to generate chloromethane. The invention is characterized in that the catalyst is gamma-Al2O3 or the gamma-Al2O3 immerged by zinc chloride while the zinc chloride content is 1-40% of catalyst mass, the reaction materials are added with at least one of hydrochloride, oxygen and chlorine gas, referring to 1mol of carbon tetrachloride, their mol ratios are 0.5-4 hydrochloride, 0.001-0.1 oxygen and 0.0001-0.05 chlorine gas, thereby improving the selectivity of chloromethane, restraining the carbon accumulation of catalyst and prolonging the service life of catalyst.
Description
Technical field
The invention belongs to the prolongation catalyst method in service life, relate to the used in preparation of methyl chloride by carbon tetrachloride alcoholysis catalyst system therefor.
Background technology
Carbon tetrachloride is the main accessory substance of methane chloride device, and it can consume the ozone layer 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 ODS such as superseded carbon tetrachloride, therefore develop carbon tetrachloride 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 butyl rubber polymerization catalyst, the extractant of heat-sensitive substance, production tetramethyl lead, methylcellulose and herbicide etc. except that carrene and chloroform are produced in further chlorination.
The reaction of used in preparation of methyl chloride by carbon tetrachloride alcoholysis is to carry out in liquid phase at present.The patent No. is that 95108577.8 Chinese patent discloses a kind of alcoholysis of carbon tetrachloride method.This method is that carbon tetrachloride and methyl alcohol are fed in the solder(ing)acid with the preparation monochloro methane, and in embodiment, the conversion ratio of its carbon tetrachloride is about 77%, and the service life of catalyst is not mentioned.
The difficult point of alcoholysis of carbon tetrachloride reaction is the stability of catalyst, and catalyst is tied charcoal easily.The problem that need to solve is to keep the stability of catalyst, has higher space-time yield and selectivity preferably again.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that prolongs life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis, guaranteeing that carbon tetrachloride has higher conversion, monochloro methane has under the higher optionally condition, and catalyst stability is good, long service life.
The present invention prolongs the method for life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis, and gas-phase reaction in the presence of catalyst generates monochloro methane by raw material carbon tetrachloride and methyl alcohol, it is characterized in that described catalyst is γ-Al
2O
3Or the γ-Al of dipping zinc chloride
2O
3The pickup of zinc chloride is 1～40% of a catalyst weight, in reaction raw materials, feed at least a gas in hydrogen chloride, oxygen and the chlorine simultaneously, in 1 mole of carbon tetrachloride, every kind of gas separately or mix and add fashionable molal quantity and be respectively: hydrogen chloride 0.5～4, oxygen 0.001～0.1, chlorine 0.0001～0.05.
The present invention relates to carbon tetrachloride and the methanol vapor phase legal system is equipped with monochloro methane, reaction equation is:
CH
3OH+HCl→CH
3Cl+H
2O
CCl
4+2H
2O→4HCl+CO
2
Overall reaction equation: CCl
4+ 4CH
3OH → 4CH
3Cl+2H
2O+CO
2
Selected catalyst is γ-Al
2O
3Or the γ-Al of dipping zinc chloride
2O
3Can be only with γ-Al
2O
3Make catalyst, 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 catalyst and can reach higher carbon tetrachloride conversion and higher monochloro methane selectivity.γ-Al with the dipping zinc chloride
2O
3Make catalyst and can reach higher carbon tetrachloride conversion.
Carbon tetrachloride, methyl alcohol by a certain percentage with gas phase continuous pass through catalyst, air speed 1～60s, its mol ratio is a carbon tetrachloride: methyl alcohol=1: 2～8, preferred mol ratio is a carbon tetrachloride: methyl alcohol=1: 3～7.Reaction temperature is 150 ℃～300 ℃, and preferred reaction temperature is 180 ℃～280 ℃, and reaction pressure is 0～0.5Mpa.
The present invention feeds a kind of gas, any two kinds of gases or three kinds of gases in a certain amount of hydrogen chloride, oxygen or the chlorine simultaneously in raw material mixture is favourable to used in preparation of methyl chloride by carbon tetrachloride alcoholysis, can improve the selectivity of monochloro methane, suppress the catalyst junction charcoal, prolong catalyst life.After feeding described gas, the selectivity of used in preparation of methyl chloride by carbon tetrachloride alcoholysis is more than 99%, and the service life of catalyst can be above four months.
Hydrogen chloride is the raw material that the methyl alcohol hydrochlorinate prepares monochloro methane, feeds the material ratio that hydrogen chloride can be regulated carbon tetrachloride and methyl alcohol in the reaction of alcoholysis of carbon tetrachloride, keeps activity of such catalysts.The mol ratio of hydrogen chloride and carbon tetrachloride limits within the specific limits, is generally carbon tetrachloride: hydrogen chloride=1: 0.5～4, preferred mol ratio is a carbon tetrachloride: hydrogen chloride=1: 0.7～3.
In the alcoholysis of carbon tetrachloride reaction raw materials, feed a certain amount of oxygen (perhaps air also can) and also can effectively suppress the knot charcoal of catalyst, keep catalyst activity preferably.Aerating oxygen can make the knot char combustion and become carbon dioxide and discharge with reaction mass.The mol ratio of carbon tetrachloride and oxygen is: carbon tetrachloride: oxygen=1: 0.001～0.1, preferred mol ratio is: carbon tetrachloride: oxygen=1: 0.005～0.05.
The present invention finds that feeding chlorine also is effective for the life-time dilatation of this catalysts.We know, the thermal chlorination reaction of chlorine and monochloro methane is carried out under about 430 ℃ and about 0.75Mpa pressure condition, so under this method condition, feeding chlorine can't be to the selectivity generation considerable influence of monochloro methane.The mol ratio of carbon tetrachloride and chlorine is: carbon tetrachloride: chlorine=1: 0.0001～0.05, preferred mol ratio is: carbon tetrachloride: chlorine=1: 0.001～0.01.
Can feed a kind of gas in hydrogen chloride, oxygen and the chlorine in the raw material of alcoholysis of carbon tetrachloride reaction, also can feed wherein any two kinds of gases or the mixture of three kinds of gases, for keeping catalyst activity, suppress the catalyst junction charcoal and all can play extraordinary effect.(1) mixture of feeding hydrogen chloride and oxygen, the mol ratio of they and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: oxygen=1: 0.05～4: 0.001～0.1, preferred mol ratio is: carbon tetrachloride: hydrogen chloride: oxygen=1: 0.07～3: 0.005～0.05.(2) mixture of feeding hydrogen chloride and chlorine, the mol ratio of they and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: chlorine=1: 0.05～4: 0.0001～0.05, preferred mol ratio is: carbon tetrachloride: hydrogen chloride: chlorine=1: 0.07～3: 0.001～0.01.(3) mixture of aerating oxygen and chlorine, the mol ratio of they and carbon tetrachloride is: carbon tetrachloride: oxygen: chlorine=1: 0.001～0.1: 0.0001～0.05, preferred mol ratio is: carbon tetrachloride: oxygen: chlorine=1: 0.005～0.05: 0.001～0.01.(4) mixture of feeding hydrogen chloride, oxygen and chlorine, the mol ratio of they and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: oxygen: chlorine=1: 0.5～4: 0.001～0.1: 0.0001～0.05, preferred mol ratio is: carbon tetrachloride: hydrogen chloride: oxygen: chlorine=1: 0.7～3: 0.005～0.05: 0.001～0.01.
Advantage of the present invention:
Carbon tetrachloride has higher conversion, the selectivity height of monochloro methane, catalyst long service life.
The specific embodiment
Describe the present invention in detail by following examples, not delimit the scope of the invention.
Embodiment 1～8:
γ-the Al of 50ml dipping 15% (accounting for total catalyst weight) zinc chloride
2O
3Catalyst is packed in the diameter 20mmInconel600 reaction tube, feed the mixture of a kind of gas, any two kinds of gases or three kinds of gases in carbon tetrachloride, methyl alcohol and hydrogen chloride, oxygen and the chlorine of vaporizing, 250 ℃ of reaction temperatures, reaction pressure 0.2Mpa, time of contact 1～60s, product is used gas chromatographic analysis through alkali cleaning, drying.Below be the analysis result (annotate: all material ratios are mol ratio, and conversion ratio and selectivity unit are mol%) that reacts 500 hours, reacted 1500 hours and reacted 2880 hours:
| Sequence number | CH 3OH/ CCl 4 | HCl/CCl 4 | O 2/CCl 4 | Cl 2/CCl 4 | Reacted 500 hours | Reacted 1500 hours | Reacted 2880 hours | |||
| CCl 4Conversion ratio | CH 3The Cl selectivity | CCl 4Conversion ratio | CH 3The Cl selectivity | CCl 4Conversion ratio | CH 3The Cl selectivity | |||||
| 1 | 4.1 | 0 | 0 | 0 | 93.5 | 98.5 | 88.5 | 81.5 | 75.0 | 70.1 |
| 2 | 5.5 | 1.5 | 0 | 0 | 94.5 | 99.5 | 94.4 | 99.5 | 94.0 | 99.0 |
| 3 | 4.1 | 0 | 0.05 | 0 | 93.8 | 98.5 | 93.7 | 98.4 | 93.0 | 97.9 |
| 4 | 4.2 | 0 | 0 | 0.0006 | 93.5 | 98.8 | 93.5 | 98.7 | 93.2 | 98.0 |
| 5 | 5.1 | 1.1 | 0.06 | 0 | 94.6 | 98.9 | 94.5 | 98.8 | 94.0 | 98.1 |
| 6 | 6.0 | 2.1 | 0 | 0.001 | 93.6 | 99.4 | 93.4 | 99.4 | 93.1 | 99.0 |
| 7 | 4.1 | 0 | 0.04 | 0.002 | 95.1 | 99.0 | 95.0 | 99.0 | 94.7 | 98.7 |
| 8 | 7.1 | 3.2 | 0.01 | 0.005 | 94.9 | 99.5 | 94.8 | 99.4 | 94.1 | 99.1 |
As can be seen from the data, when only feeding raw material carbon tetrachloride and methyl alcohol, flood the γ-Al of 15% zinc chloride
2O
3Catalyst conversion ratio and selectivity descend very fast, and the catalyst junction charcoal is more serious.The mixture that feeds a kind of gas, any two kinds of gases or three kinds of gases in hydrogen chloride, oxygen and the chlorine all can suppress the catalyst junction charcoal, prolongs catalyst life.
Embodiment 9～16:
50ml γ-Al
2O
3Catalyst is packed in the diameter 20mm Incone1600 reaction tube, feed the mixture of a kind of gas, any two kinds of gases or three kinds of gases in carbon tetrachloride, methyl alcohol and hydrogen chloride, oxygen and the chlorine of vaporizing, 280 ℃ of reaction temperatures, reaction pressure 0.3Mpa, time of contact 1～60s, product is used gas chromatographic analysis through alkali cleaning, drying.Below be the analysis result (annotate: all material ratios are mol ratio, and conversion ratio and selectivity unit are mol%) that reacts 500 hours, reacted 1500 hours and reacted 2880 hours:
| Sequence number | CH 3OH/ CCl 4 | HCl/CCl 4 | O 2/CCl 4 | Cl 2/CCl 4 | Reacted 500 hours | Reacted 1500 hours | Reacted 2880 hours | |||
| CCl 4Conversion ratio | CH 3The Cl selectivity | CCl 4Conversion ratio | CH 3The Cl selectivity | CCl 4Conversion ratio | CH 3The Cl selectivity | |||||
| 1 | 4.1 | 0 | 0 | 0 | 93.0 | 98.1 | 86.6 | 79.7 | 73.4 | 69.7 |
| 2 | 5.0 | 1.1 | 0 | 0 | 93.5 | 98.5 | 93.4 | 98.5 | 93.1 | 98.0 |
| 3 | 4.1 | 0 | 0.07 | 0 | 92.8 | 98.5 | 92.7 | 98.4 | 92.0 | 97.9 |
| 4 | 4.5 | 0 | 0 | 0.001 | 92.9 | 97.8 | 92.5 | 97.7 | 92.2 | 97.3 |
| 5 | 5.1 | 1.1 | 0.06 | 0 | 93.5 | 97.9 | 93.5 | 97.8 | 93.0 | 97.2 |
| 6 | 6.0 | 2.0 | 0 | 0.001 | 92.9 | 98.4 | 92.4 | 98.4 | 92.2 | 98.1 |
| 7 | 4.0 | 0 | 0.04 | 0.002 | 93.1 | 98.1 | 93.0 | 98.0 | 93.0 | 97.7 |
| 8 | 5.3 | 1.3 | 0.01 | 0.005 | 94.6 | 99.5 | 94.6 | 99.5 | 94.2 | 99.0 |
As can be seen from the data, when only feeding raw material carbon tetrachloride and methyl alcohol, γ-Al
2O
3Catalyst conversion ratio and selectivity descend also very fast, and the catalyst junction charcoal is more serious.The mixture that feeds a kind of gas, any two kinds of gases or three kinds of gases in hydrogen chloride, oxygen and the chlorine can play and suppress the catalyst junction charcoal, the effect that prolongs catalyst life.
Embodiment 17:
According to embodiment 1, in tubular reactor, adopt the γ-Al of dipping 25% zinc chloride
2O
3Make catalyst, carbon tetrachloride, methyl alcohol and hydrogen chloride raw materials components mole ratio are 1: 3: 0.5,260 ℃ of reaction temperatures, and during reaction pressure 0.3Mpa, assay products, can calculate carbon tetrachloride conversion is 88%, the monochloro methane selectivity is 99%.
Embodiment 18:
According to embodiment 1, in tubular reactor, adopt the γ-Al of dipping 8% zinc chloride
2O
3Make catalyst, carbon tetrachloride, methyl alcohol, oxygen, chlorine feed mol ratio are 1: 2: 0.1: 0.03, and 240 ℃ of reaction temperatures, during reaction pressure 0.5Mpa, assay products, can calculate carbon tetrachloride conversion is 90%, the monochloro methane selectivity is 98%.
Embodiment 19:
According to embodiment 1, in tubular reactor, adopt the γ-Al of dipping 35% zinc chloride
2O
3Make catalyst, the raw materials components mole ratio of carbon tetrachloride, methyl alcohol, hydrogen chloride, oxygen is 1: 8: 4: 0.1, and 270 ℃ of reaction temperatures, during reaction pressure 0.3Mpa, assay products, can calculate carbon tetrachloride conversion is 94%, the monochloro methane selectivity is 99%.
Embodiment 20:
According to embodiment 1, in tubular reactor, adopt γ-Al
2O
3Make catalyst, carbon tetrachloride, methyl alcohol, hydrogen chloride, oxygen, chlorine feed mol ratio are 1: 5.5: 0.9: 0.07: 0.05, and 290 ℃ of reaction temperatures, during reaction pressure 0.25Mpa, assay products, can calculate carbon tetrachloride conversion is 90%, the monochloro methane selectivity is 99%.
Claims (10)
1, a kind of method that prolongs life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis, gas-phase reaction in the presence of catalyst generates monochloro methane by raw material carbon tetrachloride and methyl alcohol, it is characterized in that described catalyst is γ-Al
2O
3Or the γ-Al of dipping zinc chloride
2O
3The pickup of zinc chloride is 1～40% of a catalyst weight, in reaction raw materials, feed at least a gas in hydrogen chloride, oxygen and the chlorine simultaneously, in 1 mole of carbon tetrachloride, every kind of gas separately or mix and add fashionable molal quantity and be respectively: hydrogen chloride 0.5～4, oxygen 0.001～0.1, chlorine 0.0001～0.05.
2, method according to claim 1 is characterized in that described reaction raw materials raw materials components mole ratio is: carbon tetrachloride: methyl alcohol=1: 2～8.
3, method according to claim 1 is characterized in that reaction temperature is 150 ℃～300 ℃, and reaction pressure is 0～0.5Mpa, and reaction velocity is 1～60s.
4. method according to claim 1 is characterized in that feeding simultaneously hydrogen chloride in reaction raw materials, the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride=1: 0.5～4.
5. method according to claim 1 is characterized in that in reaction raw materials aerating oxygen simultaneously, and the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: oxygen=1: 0.001～0.01.
6. method according to claim 1 is characterized in that feeding simultaneously chlorine in reaction raw materials, the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: chlorine=1: 0.0001～0.05.
7. method according to claim 1 is characterized in that feeding simultaneously hydrogen chloride and oxygen in reaction raw materials, the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: oxygen=1: 0.05～4: 0.001～0.1.
8. method according to claim 1 is characterized in that feeding simultaneously hydrogen chloride and chlorine in reaction raw materials, the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: chlorine=1: 0.05～4: 0.0001～0.05.
9. method according to claim 1 is characterized in that in reaction raw materials aerating oxygen and chlorine simultaneously, and the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: oxygen: chlorine=1: 0.001～0.1: 0.0001～0.05.
10. method according to claim 1, it is characterized in that feeding simultaneously in reaction raw materials hydrogen chloride, oxygen and chlorine, the mol ratio of itself and carbon tetrachloride is: carbon tetrachloride: hydrogen chloride: oxygen: chlorine=1: 0.5～4: 0.001～0.1: 0.0001～0.05.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100423321A CN100409942C (en) | 2006-02-08 | 2006-02-08 | Method for extending life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis |
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|---|---|---|---|
| CNB2006100423321A CN100409942C (en) | 2006-02-08 | 2006-02-08 | Method for extending life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis |
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| Publication Number | Publication Date |
|---|---|
| CN101015809A true CN101015809A (en) | 2007-08-15 |
| CN100409942C CN100409942C (en) | 2008-08-13 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657486A (en) * | 2020-12-13 | 2021-04-16 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing methane chloride from methanol by gas phase method |
| CN116196965A (en) * | 2023-04-25 | 2023-06-02 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183797A (en) * | 1990-05-24 | 1993-02-02 | The Dow Chemical Company | Catalyst for hydrohalogenation of hydrocarbons |
| US5180700A (en) * | 1991-05-13 | 1993-01-19 | Dowelanco | Regeneration and extension of lifetime of dehydrogenation catalysts used in the preparation of 2-alkylpyrimidines |
| CN1069720A (en) * | 1991-08-22 | 1993-03-10 | 陶氏化学公司 | The method of hydrohalogenation of hydrocarbons and catalyzer |
| US5763729A (en) * | 1994-11-14 | 1998-06-09 | Uop | Alkylation of alkanes with alkyl halides |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657486A (en) * | 2020-12-13 | 2021-04-16 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing methane chloride from methanol by gas phase method |
| CN116196965A (en) * | 2023-04-25 | 2023-06-02 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
| CN116196965B (en) * | 2023-04-25 | 2023-08-15 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
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