CN101875604B - Method for performing liquid-phase partial oxidation on methane - Google Patents
Method for performing liquid-phase partial oxidation on methane Download PDFInfo
- Publication number
- CN101875604B CN101875604B CN 200910083270 CN200910083270A CN101875604B CN 101875604 B CN101875604 B CN 101875604B CN 200910083270 CN200910083270 CN 200910083270 CN 200910083270 A CN200910083270 A CN 200910083270A CN 101875604 B CN101875604 B CN 101875604B
- Authority
- CN
- China
- Prior art keywords
- methane
- partial oxidation
- performing liquid
- phase partial
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a method for performing liquid-phase partial oxidation on methane, and belongs to the field of methane conversion. The method is characterized in that: potassium tetrachloropalladate and molybdovanadophosphoric heteropolyacid are used as catalysts and oxygen is used as an oxidant in a trifluoroacetic acid solvent; and the methane is oxidized to form acetic acid and methyl trifluoroacetate. In the method, the molar ratio of the potassium tetrachloropalladate to the molybdovanadophosphoric heteropolyacid serving as the catalysts is 500:1-0.01:1; the concentration of the potassium tetrachloropalladate and the molybdovanadophosphoric heteropolyacid is respectively 0.01 to 5mm and 0.01 to 1mm; the total pressure of the methane and oxygen is 2.5 to 5.0MPa; the partial pressure ratio of the methane to the oxygen is (0.5-10):1; and reaction is performed for 1 to 15 hours at the temperature of between 40 and 120 DGE C to form the acetic acid and methyl trifluoroacetate. The conversion rate of the methane can reach 23.04 percent; and the method is favorable for solving the problems of high price and toxicity of the catalyst and the like in the liquid-phase oxidation reaction of the methane.
Description
Technical field
The present invention relates to a kind of method of performing liquid-phase partial oxidation on methane, belong to the methane conversion technical field.
Background technology
Methane is the main component of Sweet natural gas, and reserves are abundant, are a kind of low value-added carbon back raw materials.Be the liquid products such as acid, aldehyde, alcohol with conversion of natural gas, not only can accelerate the development and use of natural gas source, and can be used as the important supplement of basic chemical industry product.The methane resource utilization is converted into gaseous methane first synthetic gas (CO+H usually
2), and then pass through synthetic other high-grade products of producing of fischer-tropsch (Fischer-Tropsch) such as liquid products such as acid, aldehyde, alcohol.But methane conversion is the process need of synthetic gas at high temperature carries out (about 850 ℃), and energy consumption is very high.
The liquid phase catalytic oxidation of methane has been obtained greater advance nearly decades, the Catalytic methane oxidation process of in acidic aqueous solution, carrying out of carrying out in early days, adopt single component precious metal salt catalyzer such as Pt (II), Pd (II), Co (III) etc., but these transition metal (such as platinum, palladium, cobalt) salt is easy to be reduced in aqueous solution catalytic process, methane conversion is very low, lacks prospects for commercial application.
In recent years, the research of catalyzed oxidation methane has obtained progress in the strong acid solvents such as the vitriol oil (or oleum), trifluoroacetic acid.HgSO
4The adding of catalyzer can increase substantially the transformation efficiency of methane to about 43%, and main by product is CO
2The people such as Periana utilize connection pyrimidine (bmpy) to develop a kind of stable platinum complex catalyst Pt (bpym) Cl as part
2Can be with lesser temps catalyzed oxidation methane (R.A.Periana in 102% oleum, D.J.Taube, S.Gamble, et al.Platinum Catalysts for the High-Yield Oxidation of Methane to a MethanolDerivative.Science, 1998,280 volumes, 560～564 pages).But the mercury salt catalyst toxicity is larger, and environmental pollution is serious, platinum complex catalyst Pt (bpym) Cl
2Price is very expensive, and these defectives bring very large difficulty for the industrialization of these class methods.
The oxygenant of using in the Catalytic methane oxidation process has Cl usually
2, K
2S
2O
4, SO
3Deng, with Cl
2For the Methane Conversion by product chloro thing of oxygenant more; With K
2S
2O
4For the reaction methane conversion of oxygenant lower; With SO
3For the Methane Conversion of oxygenant exists the catalyzer turn over number lower, by product SO
2Recycling also be urgent problem.Oxygen is a kind of cheapness, eco-friendly oxygenant, has very strong magnetism take oxygen as the oxygenant oxidizing of methylene.
Summary of the invention
The invention provides the method for performing liquid-phase partial oxidation on methane under a kind of lesser temps, it is characterized in that adopting potassium palladochloride and molybdovanaphosphoric acid to make catalyzer, take oxygen as oxygenant, is acetic acid and trifluoro-acetate with methane portion oxidation.
The method comprises the steps: in the trifluoroacetic acid solvent, and catalyzer potassium palladochloride and molybdovanaphosphoric acid were added in 500: 1 in molar ratio～0.01: 1, and wherein, potassium palladochloride and molybdovanaphosphoric acid concentration are respectively 0.01～5mM and 0.01～1mM; Pass into methane and oxygen that total pressure is 2.0～5.0MPa, the intrinsic standoff ratio of methane and oxygen is (0.5～10): 1; Stir, behind 40～120 ℃ of isothermal reaction 1～15h, generate acetic acid and trifluoro-acetate, wherein, the trifluoro-acetate hydrolysis can get methyl alcohol.
It is catalyzer that the present invention adopts palladium salt and molybdovanaphosphoric acid, take oxygen cheapness, eco-friendly as oxygenant, compares with previous methods, and the toxicity problem of having avoided the mercury salt catalyzer to bring is compared with the platinum complex catalyst of costliness, decrease cost.
Embodiment
The invention will be further described below in conjunction with embodiment.
Methane and oxygen purity are respectively 99.9% and 99.995% among the embodiment.
Embodiment 1
In the 20ml trifluoroacetic acid, add 3.47mg molybdovanaphosphoric acid H
5PMo
10V
2O
40(0.1mM), 6.53mg potassium palladochloride K
2PdCl
4(1mM), 58.44mg sodium-chlor (50mM).Said mixture is added with in the teflon-lined stainless steel cauldron (50ml), pass into 1MPa methane, exhaust repeats this operation 3 times.Start magnetic agitation, pass into methane and the 1.5MPa oxygen of 1.5MPa.Behind 80 ℃ of reactions of constant temperature 8h, cool off reactor with frozen water, collect liquid phase reaction liquid, use gas chromatographic analysis, recording acetic acid concentration is 112.86mM, and trifluoro-acetate concentration is 2.38mM, and methane conversion is 23.04%.
Embodiment 2
In the 20ml trifluoroacetic acid, add 3.47mg molybdovanaphosphoric acid H
5PMo
10V
2O
40(0.1mM), 3.26mg potassium palladochloride K
2PdCl
4(0.5mM), 2.92mg sodium-chlor (2.5mM).Said mixture is added with in the teflon-lined stainless steel cauldron, pass into 1MPa methane, exhaust repeats this operation 3 times.Start magnetic agitation, pass into methane and the 1.5MPa oxygen of 1.5MPa.Behind 80 ℃ of reactions of constant temperature 8h, cool off reactor with frozen water, collect liquid phase reaction liquid, use gas chromatographic analysis, recording acetic acid concentration is 107.40mM, and trifluoro-acetate concentration is 0.77mM, and methane conversion is 21.77%.
Embodiment 3
With 20ml potassium palladochloride K
2PdCl
4Concentration is 0.05mM, molybdovanaphosphoric acid H
5PMo
10V
2O
40Concentration is 0.05mM, and sodium chloride concentration is that the reaction solution of 2.5mM adds with in the teflon-lined stainless steel cauldron, passes into 1MPa methane, and exhaust repeats this operation 3 times.Start magnetic agitation, pass into the methane of 3.0MPa and the oxygen of 0.5MPa.Behind 80 ℃ of reactions of constant temperature 8h, cool off reactor with frozen water, collect liquid phase reaction liquid, use gas chromatographic analysis, recording acetic acid concentration is 76.18mM, and trifluoro-acetate concentration is 3.38mM, and methane conversion is 7.87%.
Embodiment 4
Molybdovanaphosphoric acid salt Na with same concentrations
3H
3PMo
9V
3O
40Replace the molybdovanaphosphoric acid H among the embodiment 3
5PMo
10V
2O
40, all the other processes and embodiment 3 are identical, and after reaction finished, the product acetic acid concentration was 51.13mM, and trifluoro-acetate concentration is 0.11mM, and methane conversion is 5.17%.
Embodiment 5
Temperature of reaction is with 80 ℃ among 120 ℃ of replacement embodiment 3, and all the other processes and embodiment 3 are identical, and after reaction finished, the product acetic acid concentration was 79.60mM, and trifluoro-acetate concentration is 1.23mM, and the transformation efficiency of methane is 8.10%.
Embodiment 6
Reaction times replaces 8h among the embodiment 3 with 15h, and all the other processes and embodiment 3 are identical, and after the reaction end, the product acetic acid concentration is 122.18mM, and trifluoro-acetate concentration is 1.17mM, and the transformation efficiency of methane is 12.40%.
Claims (8)
1. the method for a performing liquid-phase partial oxidation on methane is characterized in that take trifluoroacetic acid as solvent, and two kinds of materials of potassium palladochloride and molybdovanaphosphoric acid are catalyzer, and methane and oxygen react, and generates acetic acid and trifluoro-acetate.
2. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, the mol ratio that it is characterized in that catalyzer potassium palladochloride and molybdovanaphosphoric acid is 500: 1～0.01: 1.
3. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, the concentration that it is characterized in that potassium palladochloride is 0.01～5mM.
4. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, the concentration that it is characterized in that molybdovanaphosphoric acid is 0.01～1mM.
5. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, it is characterized in that molybdovanaphosphoric acid is the molybdovanaphosphoric acid of the Keggin structure of 1～4 vanadium atom replacement.
6. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, the temperature that it is characterized in that reaction system is 40～120 ℃.
7. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, it is characterized in that the reaction times is 1～15h.
8. by the method for performing liquid-phase partial oxidation on methane claimed in claim 1, it is characterized in that the initial total pressure of methane and oxygen is 2.0～5.0MPa, the intrinsic standoff ratio of methane and oxygen is (0.5～10): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910083270 CN101875604B (en) | 2009-04-30 | 2009-04-30 | Method for performing liquid-phase partial oxidation on methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910083270 CN101875604B (en) | 2009-04-30 | 2009-04-30 | Method for performing liquid-phase partial oxidation on methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101875604A CN101875604A (en) | 2010-11-03 |
| CN101875604B true CN101875604B (en) | 2013-04-24 |
Family
ID=43018300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910083270 Expired - Fee Related CN101875604B (en) | 2009-04-30 | 2009-04-30 | Method for performing liquid-phase partial oxidation on methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101875604B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747847B (en) * | 2020-06-29 | 2021-07-16 | 中山大学 | Method for alkane selective catalytic oxidation reaction |
| CN115093324B (en) * | 2022-02-22 | 2023-12-26 | 上海交通大学 | Preparation method of esterified alkane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726082A (en) * | 2002-10-23 | 2006-01-25 | 高等技术学院 | Catalysts and process for the direct conversion of methane into acetic acid |
-
2009
- 2009-04-30 CN CN 200910083270 patent/CN101875604B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726082A (en) * | 2002-10-23 | 2006-01-25 | 高等技术学院 | Catalysts and process for the direct conversion of methane into acetic acid |
Non-Patent Citations (8)
| 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》;20001231;第194-195卷;13-20 * |
| Direct oxidation of methane to acetic acid catalyzed by Pd2+ and Cu2+ in the presence of molecular oxygen;Mark Zerella,et al.;《Chem. Commun.》;20040803;1948-1949 * |
| Keggin结构和Dawson结构磷钼酸及磷钼钒酸的氧化还原特性;井淑波等;《吉林大学学报(理学版)》;20031031;第41卷(第4期);534-537 * |
| Mark Zerella,et al..Direct oxidation of methane to acetic acid catalyzed by Pd2+ and Cu2+ in the presence of molecular oxygen.《Chem. Commun.》.2004,1948-1949. |
| 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);5940-5944 * |
| 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13-20. |
| 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),5940-5944. |
| 井淑波等.Keggin结构和Dawson结构磷钼酸及磷钼钒酸的氧化还原特性.《吉林大学学报(理学版)》.2003,第41卷(第4期),534-537 . |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101875604A (en) | 2010-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Z scheme system ZnIn2S4/RGO/BiVO4 for hydrogen generation from water splitting and simultaneous degradation of organic pollutants under visible light | |
| Liu et al. | Turning waste into wealth: sustainable production of high-value-added chemicals from catalytic coupling of carbon dioxide and nitrogenous small molecules | |
| US9193593B2 (en) | Hydrogenation of formic acid to formaldehyde | |
| CN109908940A (en) | A kind of M@CN composite catalyzing material of N doping porous carbon carried metal, preparation method and application | |
| CN105218289B (en) | A kind of method that unrighted acid original position hydrogenation decarboxylation prepares long chain alkane | |
| US20230256423A1 (en) | Modified copper-zinc catalysts and methods for alcohol production from carbon dioxide | |
| Jiang et al. | Photocatalytic aldehydes/alcohols/toluenes oxidative amidation over bifunctional Pd/MOFs: Effect of Fe-O clusters and Lewis acid sites | |
| CN107473183A (en) | The application of phosphating sludge catalyzing manufacturing of hydrogen in alkaline formaldehyde solution | |
| CN103145545B (en) | A kind of method preparing hydroxymalonic acid for glycerol catalysis oxidation | |
| CN100586922C (en) | Preparation of acrylic acid | |
| Yusuf et al. | Catalytic CO2 conversion to C1 value-added products: Review on latest catalytic and process developments | |
| CN101875604B (en) | Method for performing liquid-phase partial oxidation on methane | |
| US20180057439A1 (en) | Process For The Sustainable Production Of Acrylic Acid | |
| CN101690894A (en) | Catalyst for synthesizing methanol by direct hydrogenation of carbon dioxide and preparation method thereof | |
| CN102086152B (en) | Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane | |
| Krishnan et al. | Carbon dioxide: No longer a global menace: A future source for chemicals | |
| CN102285864B (en) | Method for producing methanol by catalytic oxidation of methane | |
| CN101357894B (en) | Method for selectively reducing preparation of arylhydroxylamine from aromatic nitro compound | |
| CN101148406B (en) | Method for preparing carboxylic acid ester by using aldehyde, alcohol and oxidizing agent as raw material | |
| US10647652B2 (en) | Process for the sustainable production of acrylic acid | |
| Yang et al. | Methane oxidation to methanol over copper-containing zeolite | |
| US20240043464A1 (en) | Apparatus and method for converting carbon dioxide to sugars | |
| US9790161B2 (en) | Process for the sustainable production of acrylic acid | |
| CN1781899A (en) | Process for preparing ethyl acetate from ethanol | |
| CN109705069A (en) | A kind of preparation method of 2,5- furandicarboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130424 Termination date: 20160430 |