CN102285864B - Method for producing methanol by catalytic oxidation of methane - Google Patents
Method for producing methanol by catalytic oxidation of methane Download PDFInfo
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- CN102285864B CN102285864B CN201010201729.7A CN201010201729A CN102285864B CN 102285864 B CN102285864 B CN 102285864B CN 201010201729 A CN201010201729 A CN 201010201729A CN 102285864 B CN102285864 B CN 102285864B
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- methane
- catalytic oxidation
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- producing methanol
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a method for producing methanol by catalytic oxidation of methane, belonging to the technical field of chemical industry. The method is characterized in that in a mixed solvent of trifluoroacetic acid and water, by taking oxygen as an oxidant and dichlorobipyridine potassium, benzoquinone and phosphorus molybdenum vanadate as catalysts, methane is subjected to catalytic oxidation so as to form methyl trifluoroacetate and methanol, and the methyl trifluroracetate is hydrolyzed so as to obtain methanol. In the method, the volume ratio of water to trifluoroacetic acid is (0-1):2, the total pressure of methanol and oxygen is 2.0-5.0 MPa, the partial pressure ratio of methanol to oxygen is (1.6-12.5):1; reaction is carried out for 1-12 hours at the temperature of 40-120 DGE C so as to generate the methyl trifluroracetate and the methanol; and when water exists, the catalysts used in the invention have higher catalytic activities.
Description
Technical field
A kind of method that the present invention relates to producing methanol by catalytic oxidation of methane, belongs to chemical technology field.
Background technology
During by methane production methyl alcohol, conventionally adopt two-step approach, first adopt the method for steam cracking to produce synthetic gas (CO+H
2), then pass through F-T synthesis reaction methanol by synthetic gas.But the process energy consumption that methane conversion is synthetic gas is very high, therefore in the urgent need to methane Direct Catalytic Oxidation methanol novel method under exploitation lesser temps.
In recent years, people have proposed the effective catalyst of a series of methane Direct Catalytic Oxidations.Some transistion metal compounds have higher catalytic activity.Platinum complex catalyst Pt (bpym) Cl that the connection pyrimidine (bmpy) of take is part
2, be the most efficient catalyzer up to now.This catalyzer can be methyl sulfate by Catalytic methane oxidation at a lower temperature in 102% oleum, methyl sulfate hydrolysis can obtain methyl alcohol (R.A.Periana, D.J.Taube, S.Gamble, et al.PlatinumCatalysts for the High-Yield Oxidation of Methane to a Methanol Derivative.Science, 1998,280 volumes, 560～564 pages).But this catalyzer is expensive; The more important thing is, the moisture content that reaction process generates significantly declines catalyst activity, to industrial application, brings very large difficulty.
Someone has studied in the mixed solvent of trifluoroacetic acid and water, the mixture of palladium metal and cupric chloride of take is catalyzer, by methane oxidation, be trifluoro-acetate and methyl alcohol, obtained higher transformation efficiency (M.Lin, T.Hogan, A.Sen.A Highly Catalytic Bimetallic System for theLow-Temperature Selective Oxidation of Methane and Lower Alkanes withDioxygen as the Oxidant.Journal of the American Chemical Society, 1997, 119 volumes, 6048～6053 pages).But it is oxygenant that this catalyzed reaction be take carbon monoxide and oxygen, and carbon monoxide is poisonous to human body.
Summary of the invention
The invention provides a kind of method of producing methanol by catalytic oxidation of methane, it is characterized in that: in the mixed solvent of trifluoroacetic acid and water composition, take oxygen as oxygenant, with the mixture of dichloro dipyridyl palladium, benzoquinones and molybdovanaphosphoric acid, it is catalyzer, by Catalytic methane oxidation, be trifluoro-acetate and methyl alcohol, trifluoro-acetate is hydrolyzed and obtains methyl alcohol; While having water to exist, catalyzer of the present invention has higher catalytic activity.
The method comprises the following steps: dichloro dipyridyl palladium, benzoquinones and molybdovanaphosphoric acid are added by a certain percentage in the mixed solvent of trifluoroacetic acid and water composition, wherein the volume ratio of water and trifluoroacetic acid is 0～1: 2; The concentration of dichloro dipyridyl palladium is 0.1～3mM; In reaction system, the mol ratio of chlorion and dichloro dipyridyl palladium is 0～100; Molybdovanaphosphoric acid is the molybdovanaphosphoric acid of the Keggin structure of 1～4 vanadium atom replacement, and the concentration of molybdovanaphosphoric acid is 0.05～3mM; Pass into methane and oxygen that total pressure is 2.0～5.0MPa, wherein the intrinsic standoff ratio of methane and oxygen is (1.6～12.5): 1; Stir, at 40～120 ℃ of isothermal reaction 1～12h, generate trifluoro-acetate and methyl alcohol; Trifluoro-acetate is hydrolyzed and obtains methyl alcohol.
While having water to exist, catalyzer of the present invention has higher catalytic activity.
Embodiment
Embodiment 1
First by dichloro dipyridyl palladium (0.30mM), benzoquinones (1.20mM) and molybdovanaphosphoric acid H
5pMo
10v
2o
40(0.05mM) be placed in the stainless steel autoclave (50mL) that glass-lined is housed, wherein reaction solvent is 10mL trifluoroacetic acid.Envelope still, gets rid of air in still with methane, finally passes into 2.5MPa methane and 0.5MPa oxygen, closes intake valve, starts magnetic agitation, in 100 ℃ of reaction 8h.After reaction stops, autoclave is placed in to mixture of ice and water and is cooled to 3 ℃ of left and right, take out reaction solution, utilize gas chromatograph to analyze the concentration of trifluoro-acetate and methyl alcohol in liquid phase.The total concn that records trifluoro-acetate and methyl alcohol is 1.12mM.
Embodiment 2
First by dichloro dipyridyl palladium (0.25mM), benzoquinones (1.00mM) and molybdovanaphosphoric acid H
5pMo
10v
2o
40(0.04mM) be placed in the stainless steel autoclave (50mL) that glass-lined is housed, wherein reaction solvent is 10mL trifluoroacetic acid and 2mL water.Envelope still, gets rid of air in still with methane, finally passes into 2.5MPa methane and 0.5MPa oxygen, closes intake valve, starts magnetic agitation, in 100 ℃ of reaction 8h.After reaction stops, autoclave is placed in to mixture of ice and water and is cooled to 3 ℃ of left and right, take out reaction solution, utilize gas chromatograph to analyze the concentration of trifluoro-acetate and methyl alcohol in liquid phase.The total concn that records trifluoro-acetate and methyl alcohol is 3.58mM.
Embodiment 3
Dichloro dipyridyl palladium, benzoquinones, the concentration of molybdovanaphosphoric acid, the composition of reaction solvent and cumulative volume, operating process are all identical with embodiment 2.In reaction system, add 15mM sodium-chlor.Subsequent step is identical with embodiment 2.After reaction stops, the concentration that records trifluoro-acetate is 7.40mM.
Embodiment 4
First by dichloro dipyridyl palladium (0.25mM), benzoquinones (1.00mM) and molybdovanaphosphoric acid H
5pMo
10v
2o
40(0.21mM) be placed in the stainless steel autoclave (50mL) that glass-lined is housed, wherein reaction solvent is 10mL trifluoroacetic acid and 2mL water.Envelope still, gets rid of air in still with methane, finally passes into 2.5MPa methane and 0.5MPa oxygen, closes intake valve, starts magnetic agitation, in 100 ℃ of reaction 8h.After reaction stops, autoclave is placed in to mixture of ice and water and is cooled to 3 ℃ of left and right, take out reaction solution, utilize gas chromatograph to analyze the concentration of trifluoro-acetate and methyl alcohol in liquid phase.The total concn that records trifluoro-acetate and methyl alcohol is 12.90mM.
Claims (7)
1. the method for a producing methanol by catalytic oxidation of methane, it is characterized in that: in the mixed solvent of trifluoroacetic acid and water composition, take oxygen as oxygenant, with the mixture of dichloro dipyridyl palladium, benzoquinones and molybdovanaphosphoric acid, it is catalyzer, by Catalytic methane oxidation, be trifluoro-acetate and methyl alcohol, trifluoro-acetate is hydrolyzed and obtains methyl alcohol; In mixed solvent, the volume ratio of water and trifluoroacetic acid is 0.4～1:2; While having water to exist, the catalyzer adopting has higher catalytic activity.
2. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: the concentration of dichloro dipyridyl palladium is 0.1～3mM.
3. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: molybdovanaphosphoric acid is the molybdovanaphosphoric acid of the Keggin structure of 1～4 vanadium atom replacement.
4. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: the concentration of molybdovanaphosphoric acid is 0.04～2.4mM.
5. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: the initial total pressure of methane and oxygen is 2.0～5.0MPa, and the intrinsic standoff ratio of methane and oxygen is (1.6～12.5): 1.
6. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: the temperature of reaction system is 40～120 ℃.
7. the method for producing methanol by catalytic oxidation of methane according to claim 1, is characterized in that: the reaction times is 1～12h.
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| CN201010201729.7A CN102285864B (en) | 2010-06-17 | 2010-06-17 | Method for producing methanol by catalytic oxidation of methane |
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| CN201010201729.7A CN102285864B (en) | 2010-06-17 | 2010-06-17 | Method for producing methanol by catalytic oxidation of methane |
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| CN102285864A CN102285864A (en) | 2011-12-21 |
| CN102285864B true CN102285864B (en) | 2014-02-05 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103949257B (en) * | 2014-04-27 | 2016-01-06 | 东北石油大学 | For the production of nucleocapsid perovskite type catalyst and the application of controllable synthesis gas |
| CN103949263B (en) * | 2014-04-27 | 2016-04-13 | 东北石油大学 | For the perovskite mixed oxides catalyst and preparation method thereof of methane methyl alcohol |
| CN115093324B (en) * | 2022-02-22 | 2023-12-26 | 上海交通大学 | Preparation method of esterified alkane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233113A (en) * | 1991-02-15 | 1993-08-03 | Catalytica, Inc. | Process for converting lower alkanes to esters |
| CN101495435A (en) * | 2006-07-04 | 2009-07-29 | 中国科学院大连化学物理研究所 | Oxiadition catalyst |
-
2010
- 2010-06-17 CN CN201010201729.7A patent/CN102285864B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233113A (en) * | 1991-02-15 | 1993-08-03 | Catalytica, Inc. | Process for converting lower alkanes to esters |
| CN101495435A (en) * | 2006-07-04 | 2009-07-29 | 中国科学院大连化学物理研究所 | Oxiadition catalyst |
Non-Patent Citations (6)
| Title |
|---|
| Catalytic performance of 11-molybdo-1-vanadophosphoric acid as a catalyst precursor and the optimization of reaction conditions for the oxidation of methane with hydrogen peroxide;Yasuhiro Seki et al;《Applied Catalysis A: General》;20000313;第194-195卷;第13-20页 * |
| Itsik Bar-Nahum et al.Mild, Aqueous, Aerobic, Catalytic Oxidation of Methane to Methanol and Acetaldehyde Catalyzed by a Supported Bipyrimidinylplatinum-Polyoxometalate Hybrid Compound.《Journal of the American Chemical Society》.2004,第126卷(第33期),第10236-10237页. |
| Mild, Aqueous, Aerobic, Catalytic Oxidation of Methane to Methanol and Acetaldehyde Catalyzed by a Supported Bipyrimidinylplatinum-Polyoxometalate Hybrid Compound;Itsik Bar-Nahum et al;《Journal of the American Chemical Society》;20040730;第126卷(第33期);第10236-10237页 * |
| Reaction Mechanism of Oxidation of Methane with Hydrogen Peroxide Catalyzed by 11-Molybdo-1-vanadophosphoric Acid Catalyst Precursor;Yasuhiro Seki et al;《J.Phys.Chem.B》;20000531;第104卷(第25期);第5940-5944页 * |
| Yasuhiro Seki et al.Catalytic performance of 11-molybdo-1-vanadophosphoric acid as a catalyst precursor and the optimization of reaction conditions for the oxidation of methane with hydrogen peroxide.《Applied Catalysis A: General》.2000,第194-195卷第13-20页. |
| Yasuhiro Seki et al.Reaction Mechanism of Oxidation of Methane with Hydrogen Peroxide Catalyzed by 11-Molybdo-1-vanadophosphoric Acid Catalyst Precursor.《J.Phys.Chem.B》.2000,第104卷(第25期),第5940-5944页. |
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