CN100348570C - Method for catalytic oxidation preparation of methyl formate from methanol - Google Patents
Method for catalytic oxidation preparation of methyl formate from methanol Download PDFInfo
- Publication number
- CN100348570C CN100348570C CNB2004100111814A CN200410011181A CN100348570C CN 100348570 C CN100348570 C CN 100348570C CN B2004100111814 A CNB2004100111814 A CN B2004100111814A CN 200410011181 A CN200410011181 A CN 200410011181A CN 100348570 C CN100348570 C CN 100348570C
- Authority
- CN
- China
- Prior art keywords
- oxygen
- methanol
- methyl
- reaction
- nitrogen
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method for preparing methyl formate by catalyzing and oxidizing methanol under an oxygenic condition. Elementary substance silver is used as catalysts, methanol vapour, oxygen and nitrogen in a standard state are led in, the range of the molar ratio of methanol to oxygen is from 3.0 to 18.5, the molar ratio of nitrogen to oxygen is from 3.0 to 17.5, the temperature range of a bed layer of a reaction bed is from 500 to 650K, the range of the air speed of catalytic reaction is from 5000h<-1> to 40000h<-1>, and oxygen exists in raw materials of catalytic reaction. The catalysts have the advantages of no need of activation, high catalytic activity and no reference to elements of chromium and cadmium with pollution to the environment.
Description
Technical field
The present invention relates to the method that a kind of catalyzed oxidation methyl alcohol prepares methyl-formiate, specifically, relating to a kind of is catalyzer prepares methyl-formiate at catalysis in aerobic condition oxidation methyl alcohol method with simple substance silver.
Background technology
Methyl-formiate is carbon one Chemicals on basis, and purposes is very extensive.The main at present raw material of production organic synthesis that is used as is as preparing formic acid, methane amide, dimethyl formamide acetate, methyl acetate, acetic anhydride, ethylene glycol, trichloromethylchloroformate etc. or solvent and preparation high-purity CO.In addition, methyl-formiate also is used as the alternative fuel of sterilant, sterilant, fumigant, agent for tobacco treatment, plastic castings low temperature smoothing agent and methanol fuel cell.
The preparation technology of methyl-formiate mainly contains four kinds of modes at present: (1) formic acid esterification method, (2) methanol carbonylation, (3) methanol dehydrogenation method, (4) synthetic gas direct synthesis technique.Methanol esterification method cost height (cost is the twice of methanol dehydrogenation method), and equipment corrosion is serious, has eliminated this method abroad.Methanol carbonylation is to be base catalyst with the basic metal carbinol compound, and methyl alcohol and carbon monoxide prepare under middle pressure, liquid-phase condition, and this method has strict requirement for the content of water in the raw material carbon monoxide and carbonic acid gas, has realized industrialization.The synthetic gas direct synthesis technique prepares the reaction that methyl-formiate is the atom economy type, but because methyl-formiate throughput is low, severe reaction conditions does not realize industrialization.
The methanol dehydrogenation method is at copper-based catalysts, tin-molybdenum composite oxides, tin-systems such as tungsten composite oxides, mainly concentrate on copper-based catalysts at present, but because copper is easy to assemble, cause that phase transformation causes inactivation, and very big relation is arranged for the catalytic activity of methyl-formiate and preparation method and activation condition.For copper-based catalysts, mainly be to improve catalyst activity and stability by adding chromium sesquioxide and basic metal or alkaline earth metal oxide.
People's such as Thomas patent report silver-cadmium composite oxides be under the condition of carrier gas with nitrogen or hydrogen, be that starting raw material prepares methyl-formiate with methyl alcohol.People such as Wachs under high vacuum condition, found can obtain methyl-formiate by methanol oxidation on the monocrystal silver surface before two more than ten years.In general, be equipped with in silver-colored legal system the catalyst system of formaldehyde, methyl-formiate is as by product and unheeded.Be equipped with in the technology of formaldehyde because the singularity of oxygen species on the metallic sliver catalyst in silver-colored legal system, in order to obtain the optimal yield of formaldehyde, industrial operation characteristics are: high reaction mass air speed, high temperature, low pure oxygen ratio.The work of Wachs shows: 1. methyl-formiate is that the formaldehyde of ADSORPTION STATE is adsorbed the methoxyl group attack of attitude and obtains false hemiacetal, and the false hemiacetal dehydrogenation of generation obtains methyl-formiate.2. the step of false hemiacetal is that the slow step of entire reaction is rapid.Show in argent catalyzed oxidation methyl alcohol prepares the research of formaldehyde: according to the pure oxygen ratio of industrial condition, the formaldehyde of generation can be continued oxidation and be generated carbonic acid gas.Experiment shows: under the high temperature aerobic conditions, methyl-formiate is very easy to be decomposed.
Heterogeneous catalyst has the characteristics of convenient separation, but the catalyst system that present heterogeneous catalyst prepares methyl-formiate has following shortcoming: (1) Cu-series catalyst preparation process and reactivation process complexity, the life-span is short, and uses the chromium element of environmental pollution.(2) cadmium element in silver-cadmium alloy is a kind of element that environment is had pollution.
Summary of the invention
The present invention provides a kind of catalyzed oxidation methyl alcohol to prepare the method for methyl-formiate in order to solve above shortcoming.What the present invention adopted is that the industrial silver-oxygen-methyl alcohol catalyst system that widely uses prepares methyl-formiate.
In order to obtain the yield of methyl-formiate preferably, catalytic reaction condition should be: low reaction mass air speed, low temperature of reaction, high pure oxygen ratio, its reaction process is: catalyst simple substance silver feeds methanol steam, oxygen, nitrogen (standard state), the molar ratio range of methyl alcohol and oxygen is 3.0 to 1 8.5, the mol ratio of nitrogen and oxygen is 3.0～17.5: 1, and reaction bed bed temperature scope is 500-650K, and the air speed scope of catalyzed reaction is 5000h
-1To 40000h
-1, methanol conversion can reach 26.9%, methyl-formiate yield 16.9%, formaldehyde yield 1.2%.
For silver-oxygen-methyl alcohol catalyst system, be different under the condition that traditional catalyzed reaction prepares formaldehyde, methyl-formiate is the catalyzed reaction principal product.The catalyzer that catalyzer and industrial silver-colored legal system are equipped with formaldehyde is general; Do not need reactivation process under the laboratory condition; Under working conditions, the active not decline of longevity test in 50 hours; Catalyzer does not relate to chromium, the cadmium element that environment is had pollution.The result has shown the possibility of producing methyl-formiate on the catalytic unit of existing silver-colored method production formaldehyde.
Embodiment
Embodiment 1: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 500K, reaction velocity 5000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 500K, feed 300 milliliters/hour of the methanol steams of standard state simultaneously, 240 milliliters/hour of the nitrogen of standard state, 60 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 20.1%, methyl-formiate yield 7.5%, formaldehyde yield 0.2%.
Embodiment 2: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 500K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 500K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 480 milliliters/hour of the nitrogen of standard state, 120 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 15.1%, methyl-formiate yield 1 1.2%, formaldehyde yield 0.1%.
Embodiment 3: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 573K, reaction velocity 1 0000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 573K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 480 milliliters/hour of the nitrogen of standard state, 120 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 26.9%, methyl-formiate yield 16.9%, formaldehyde yield 1.2%.
Embodiment 4: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 650K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 650K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 480 milliliters/hour of the nitrogen of standard state, 120 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 23.4%, methyl-formiate yield 14.0%, formaldehyde yield 3.5%.
Embodiment 5: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 573K, reaction velocity 20000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 573K, feed 1200 milliliters/hour of the methanol steams of standard state simultaneously, 960 milliliters/hour of the nitrogen of standard state, 240 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 23.6%, methyl-formiate yield 15.8%, formaldehyde yield 1.5%.
Embodiment 6: the mol ratio of methyl alcohol and oxygen is 5.0: 1, and the mol ratio of nitrogen and oxygen is 4.0: 1, reaction bed bed temperature 573K, reaction velocity 40000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 573K, feed 2400 milliliters/hour of the methanol steams of standard state simultaneously, 1920 milliliters/hour of the nitrogen of standard state, 480 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 30.2%, methyl-formiate yield 14.9%, formaldehyde yield 8.3%.
Embodiment 7: the mol ratio of methyl alcohol and oxygen is 3.0: 1, and the mol ratio of nitrogen and oxygen is 3.0: 1, reaction bed bed temperature 500K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 500K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 450 milliliters/hour of the nitrogen of standard state, 150 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 28.7%, methyl-formiate yield 5.4%, formaldehyde yield 0.3%.
Embodiment 8: the mol ratio of methyl alcohol and oxygen is 9.0: 1, and the mol ratio of nitrogen and oxygen is 8.0: 1, reaction bed bed temperature 500K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 500K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 533 milliliters/hour of the nitrogen of standard state, 67 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 11.3%, methyl-formiate yield 7.1%, formaldehyde yield 0.01%.
Embodiment 9: the mol ratio of methyl alcohol and oxygen is 9.0: 1, and the mol ratio of nitrogen and oxygen is 8.0: 1, reaction bed bed temperature 573K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0, granularity are the 60-80 order, and catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 573K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 533 milliliters/hour of the nitrogen of standard state, 67 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 15.4%, methyl-formiate yield 12.9%, formaldehyde yield 0.7%.
Embodiment 10: the mol ratio of methyl alcohol and oxygen is 9.0: 1, and the mol ratio of nitrogen and oxygen is 8.0: 1, reaction bed bed temperature 650K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 650K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 533 milliliters/hour of the nitrogen of standard state, 67 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 12.1%, methyl-formiate yield 7.5%, formaldehyde yield 3.1%.
Embodiment 11: the mol ratio of methyl alcohol and oxygen is 18.5: 1, and the mol ratio of nitrogen and oxygen is 17.5: 1, reaction bed bed temperature 500K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 500K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 567.6 milliliters/hour of the nitrogen of standard state, 32.4 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 6.2%, methyl-formiate yield 4.5%, formaldehyde yield 0.01%.
Embodiment 12: the mol ratio of methyl alcohol and oxygen is 1 8.5: 1, and the mol ratio of nitrogen and oxygen is 17.5: 1, reaction bed bed temperature 573K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 573K, feed 600 milliliters/hour of the methanol steams () of standard state simultaneously, 567.6 milliliters/hour of the nitrogen of standard state, 32.4 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 7.2%, methyl-formiate yield 6.5%, formaldehyde yield 0.3%.
Embodiment 13: the mol ratio of methyl alcohol and oxygen is 18.5: 1, and the mol ratio of nitrogen and oxygen is 17.5: 1, reaction bed bed temperature 650K, reaction velocity 10000h
-1
Operation: simple substance silver 1.0 grams, granularity is the 60-80 order, catalyst volume is 0.12 milliliter, the reaction bed bed temperature is 650K, feed 600 milliliters/hour of the methanol steams of standard state simultaneously, 567.6 milliliters/hour of the nitrogen of standard state, 32.4 milliliters/hour of the oxygen of standard state.Experimental result is: methanol conversion 4.7%, methyl-formiate yield 3.2%, formaldehyde yield 1.3%.
Claims (1)
1. a catalysis in aerobic condition oxidation methyl alcohol prepares the preparation method of methyl-formiate, it is characterized in that catalyzer is a simple substance silver, feed methanol steam, oxygen and the nitrogen of standard state, wherein the mol ratio of methyl alcohol and oxygen is 3.0～18.5: 1, the mol ratio of nitrogen and oxygen is 3.0～17.5: 1, the bed temperature scope of reaction bed is 500～650K, and the air speed scope of catalyzed reaction is 5000h
-1To 40000h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100111814A CN100348570C (en) | 2004-10-26 | 2004-10-26 | Method for catalytic oxidation preparation of methyl formate from methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100111814A CN100348570C (en) | 2004-10-26 | 2004-10-26 | Method for catalytic oxidation preparation of methyl formate from methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1629125A CN1629125A (en) | 2005-06-22 |
| CN100348570C true CN100348570C (en) | 2007-11-14 |
Family
ID=34845575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100111814A Expired - Fee Related CN100348570C (en) | 2004-10-26 | 2004-10-26 | Method for catalytic oxidation preparation of methyl formate from methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100348570C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434538B (en) * | 2007-11-14 | 2012-03-21 | 中国科学院大连化学物理研究所 | Method for converting fatty into ester by direct catalytic oxidation |
| CN101985103B (en) * | 2010-07-26 | 2013-03-27 | 北京大学 | Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof |
| CN103922929B (en) * | 2014-04-18 | 2016-01-27 | 内蒙古大学 | A kind of preparation of supported nano-Au catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl-formiate and application thereof |
| CN103896765B (en) * | 2014-04-18 | 2016-05-25 | 内蒙古大学 | Preparation and the application thereof of the loaded nano Ag catalyst of the synthetic methyl formate of a kind of gas-phase photocatalysis partial oxidation methyl alcohol |
| CN112939777A (en) * | 2021-03-30 | 2021-06-11 | 上海簇睿低碳能源技术有限公司 | Continuous reaction device and process for preparing methyl formate through one-step oxidation of methanol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4450301A (en) * | 1982-10-21 | 1984-05-22 | Celanese Corporation | Process for converting methanol to formaldehyde |
| EP0252846A1 (en) * | 1986-07-08 | 1988-01-13 | Sollac | Catalyst for the synthesis of methanol, and its use in the synthesis of methanol |
| JPH0456015B2 (en) * | 1983-08-22 | 1992-09-07 | Shinnenryoyu Kaihatsu Gijutsu Kenkyu Kumiai | |
| CN1066264A (en) * | 1992-02-24 | 1992-11-18 | 华南理工大学 | The Formaldehyde Production method of less energy-consumption |
| WO1995000441A1 (en) * | 1993-06-17 | 1995-01-05 | The University Of Queensland | Kaolin derivatives |
| CN1390639A (en) * | 2002-06-13 | 2003-01-15 | 复旦大学 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
-
2004
- 2004-10-26 CN CNB2004100111814A patent/CN100348570C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4450301A (en) * | 1982-10-21 | 1984-05-22 | Celanese Corporation | Process for converting methanol to formaldehyde |
| JPH0456015B2 (en) * | 1983-08-22 | 1992-09-07 | Shinnenryoyu Kaihatsu Gijutsu Kenkyu Kumiai | |
| EP0252846A1 (en) * | 1986-07-08 | 1988-01-13 | Sollac | Catalyst for the synthesis of methanol, and its use in the synthesis of methanol |
| CN1066264A (en) * | 1992-02-24 | 1992-11-18 | 华南理工大学 | The Formaldehyde Production method of less energy-consumption |
| WO1995000441A1 (en) * | 1993-06-17 | 1995-01-05 | The University Of Queensland | Kaolin derivatives |
| CN1390639A (en) * | 2002-06-13 | 2003-01-15 | 复旦大学 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
Non-Patent Citations (3)
| Title |
|---|
| Methyl Formate on Ag(111). 1. Thermal Adsorption-DesorptionCharacteristics and Alignment in Monolayers.. Schwaner,A. L.,ET AL. J. Phys. Chem. B,Vol.101 No.51. 1997 * |
| Methyl formate on Ag(111). 2. Electron-induced surfacereactions.. Schwaner,A. L.,ET AL. J. Phys. Chem. B,Vol.101 No.51. 1997 * |
| The oxidation of methanol on a silver (110) catalyst.. Wachs,Israel E.,ET AL. Surf. Sci.,Vol.76 No.2. 1978 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1629125A (en) | 2005-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613274B (en) | Method for preparing methyl acetate by carbonylating dimethyl ether | |
| Thompson | Using gold nanoparticles for catalysis | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN101407448B (en) | Method for continuously preparing 1,3-propanediol by one-step glycerol conversion | |
| CN101397282B (en) | Method for preparing epoxypropane | |
| KR20090095892A (en) | Process for preparing monohydric alcohols from monocarboxylic acids or derivatives thereof | |
| CA2268663A1 (en) | Improved process for the production of supported palladium-gold catalysts | |
| CN103055851A (en) | Catalyst for synthesizing oxalic ester through oxidative coupling of CO gas phase as well as preparation and application method thereof | |
| CN100348570C (en) | Method for catalytic oxidation preparation of methyl formate from methanol | |
| CN102580754A (en) | Catalyst for synthesizing methyl acetate as well as preparation method and application | |
| CN100503039C (en) | Nanometer copper base catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxy methyl propionate and its preparation method | |
| CN101249434A (en) | Methane transform preparing ethylene and preparation of dual-function catalyst of synthesis gas | |
| CN102989459B (en) | Catalyst for preparing epsilon-caprolactone by oxidizing cyclohexanone/oxygen under aldehyde-assisted oxidizing action | |
| CN101993353B (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN100484629C (en) | Method for catalytic oxidation of saturated hydrocarbons compound | |
| CN1535947A (en) | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound | |
| CN106040246A (en) | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol | |
| KR20010095500A (en) | Preparation method of gamma butyrolactone using maleic anhydride | |
| CN108017509B (en) | The method of butadiene production 1,4- butanediol | |
| CN108929224A (en) | A method of preparation 5- hydroxyl methyl is catalyzed using bifunctional catalyst | |
| CN113731413A (en) | MOFs (metal organic frameworks) limited-area metal catalyst and preparation method and application thereof | |
| CN110981698B (en) | Preparation method of 3-methyl-2-butenol | |
| CN113134362A (en) | Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof | |
| CN100569788C (en) | Rhodium acetic anhydride complex and preparation method thereof and application | |
| LV14079B (en) | The method of glyceric acid selective preparation and catalysts for its realization |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071114 Termination date: 20101026 |