CN102442901A - Method for producing dimethyloxalate - Google Patents
Method for producing dimethyloxalate Download PDFInfo
- Publication number
- CN102442901A CN102442901A CN2010105100332A CN201010510033A CN102442901A CN 102442901 A CN102442901 A CN 102442901A CN 2010105100332 A CN2010105100332 A CN 2010105100332A CN 201010510033 A CN201010510033 A CN 201010510033A CN 102442901 A CN102442901 A CN 102442901A
- Authority
- CN
- China
- Prior art keywords
- methyl nitrite
- dimethyloxalate
- dimethyl oxalate
- generate
- gas
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing dimethyloxalate, comprising the steps of 1, reacting NO with O2 at 0.1-0.3 MPa and 20-50 degrees centigrade, generating N2O3; 2, enabling N2O3 to enter a rectifying tower, reacting with methanol at 1.0-0.3 MPa and 40-80 degrees centigrade to generate methyl nitrite, and then collecting gaseous methyl nitrite; 3, reacting methyl nitrite with CO by a palladium catalyst to generate dimethyloxalate and NO; condensing the product and separating gas and liquid, obtaining dimethyloxalate; recycling the NO gas in the first step. The method for producing dimethyloxalate reduces safety risks.
Description
Technical field
The present invention relates to a kind of method of producing dimethyl oxalate.
Background technology
Oxalic acid and barkite are important Organic Chemicals, are used for fine chemistry industry in a large number and prepare various dyestuffs medical, important solvent, extraction agent and various midbody.Get into 21 century, barkite receives as degradable environment-friendly engineering plastics monomer in the world and paying attention to widely.In addition, the barkite low-voltage hydrogenation can prepare important chemical material terepthaloyl moietie, and the normal pressure hydrolyzable makes oxalic acid, and normal pressure ammonia is separated and can be got high quality capim gordura acid amides.Barkite can also be used as solvent, produces medicine and medicine intermediate etc., for example carries out various condensation reactions with fatty ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize pharmaceutically relatively harsher as the thymine carbon monoxide liquid phase method synthesis of oxalate condition of hormone, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer is prone to run off in the reaction process.Middle 1960s; The Donald M.Fenton of U.S. Union Oil Company etc. are when studying platinum metals liquid-phase catalysis reaction; Discovery is in oxidizing atmosphere; In reaction system, add a kind of molysite or mantoquita as redox agent, ethene, carbon monoxide and methyl alcohol generation oxidative coupling reaction generate succinate.Find simultaneously then to generate barkite if from reaction system, remove ethene.Owing in oxidizing atmosphere, react, the security requirement of reaction process is very high.
Summary of the invention
The method that the purpose of this invention is to provide a kind of safe production dimethyl oxalate.
The method of production dimethyl oxalate provided by the present invention comprises the steps:
The first step: NO and O
2React 0.1～0.3Mpa, 20～50 ℃, generate N
2O
3
Second step: the N
2O
3Get into the inherent 0.1～0.3Mpa of reaction fractionating tower, 40～80 ℃ and methyl alcohol reaction generation methyl nitrite, collect the gaseous state methyl nitrite;
The 3rd step: methyl nitrite and CO react generation dimethyl oxalate and NO on palladium catalyst, condensation, carry out gas-liquid separation, obtain dimethyl oxalate, the recycle of NO gas to the first step.
The method of production dimethyl oxalate of the present invention, wherein: NO, O
2, CO, methyl alcohol mol ratio be (4～5): (0.5～1): (6～10): (20～80).
The method of production dimethyl oxalate of the present invention avoids purity oxygen directly to mix with methyl alcohol, reduces security risk.Increase the reaction times of oxygen in the first step, guarantee the oxygen complete reaction, prevent that trace oxygen is mixed in the methyl nitrite, get in the dimethyl oxalate reactor drum side reaction takes place, cause temperature runaway to burn catalyzer.
Embodiment
Embodiment 1,
The first step: 4 moles of NO and 0.5 mole of O
2React 0.3Mpa, 50 ℃, generate N
2O
3
Second step: the N
2O
3In the entering reaction fractionating tower, under 0.1Mpa, 40 ℃, generate methyl nitrite and water, utilize the chilled brine of rectifying tower top that the intravital water of gas is condensed, obtain methyl nitrite with the reaction of 20 mole, of methanol.
The 3rd step: methyl nitrite and 6 moles of CO react on palladium catalyst and generate dimethyl oxalate and NO, isolate dimethyl oxalate through condensing surface and gas-liquid separator, the recycle of NO gas to the first step.
Calculate with CO, the yield of dimethyl oxalate reaches 94%.
Embodiment 2,
The first step: 5 moles of NO and 1 mole of O
2React 0.1Mpa, 20 ℃, generate N
2O
3
Second step: the N
2O
3In the entering reaction fractionating tower, under 0.3Mpa, 70 ℃, generate methyl nitrite and water, utilize the chilled brine of rectifying tower top that the intravital water of gas is condensed, obtain methyl nitrite with the reaction of 80 mole, of methanol.
The 3rd step: methyl nitrite and 8 moles of CO react on palladium catalyst and generate dimethyl oxalate and NO, isolate dimethyl oxalate through condensing surface and gas-liquid separator, and NO is to the first step recycle.
Calculate with CO, the yield of dimethyl oxalate reaches 92%.
Embodiment 3,
The first step: 4 moles of NO and 1 mole of O
2React 0.1Mpa, 50 ℃, generate N
2O
3
Second step: the N
2O
3In the entering reaction fractionating tower, under 0.3Mpa, 80 ℃, generate methyl nitrite and water, utilize the chilled brine of rectifying tower top that the intravital water of gas is condensed, obtain methyl nitrite with the reaction of 55 mole, of methanol.
The 3rd step: methyl nitrite and 10 moles of CO react on palladium catalyst and generate dimethyl oxalate and NO, isolate dimethyl oxalate through condensing surface and gas-liquid separator, and NO is to the first step recycle.
Calculate with CO, the yield of dimethyl oxalate reaches 96%.
Above embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (2)
1. produce the method for dimethyl oxalate, comprise the steps:
The first step: NO and O
2React 0.1～0.3Mpa, 20～50 ℃, generate N
2O
3
Second step: the N
2O
3Get into the inherent 0.1～0.3Mpa of reaction fractionating tower, 40～80 ℃ and methyl alcohol reaction generation methyl nitrite, collect the gaseous state methyl nitrite;
The 3rd step: methyl nitrite and CO react generation dimethyl oxalate and NO on palladium catalyst, condensation, carry out gas-liquid separation, obtain dimethyl oxalate, the recycle of NO gas to the first step.
2. method according to claim 1 is characterized in that: NO, O
2, CO, methyl alcohol mol ratio be (4～5): (0.5～1): (6～10): (20～80).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105100332A CN102442901A (en) | 2010-10-15 | 2010-10-15 | Method for producing dimethyloxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105100332A CN102442901A (en) | 2010-10-15 | 2010-10-15 | Method for producing dimethyloxalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102442901A true CN102442901A (en) | 2012-05-09 |
Family
ID=46005887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105100332A Pending CN102442901A (en) | 2010-10-15 | 2010-10-15 | Method for producing dimethyloxalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102442901A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945262A (en) * | 2014-03-28 | 2015-09-30 | 中国科学院大连化学物理研究所 | Method for preparing prepare methyl nitrite by catalyzing methanol to reduce dilute nitric acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN101096340A (en) * | 2006-06-27 | 2008-01-02 | 上海焦化有限公司 | Process for the preparation of C1-C4-alkyl nitrites |
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
-
2010
- 2010-10-15 CN CN2010105100332A patent/CN102442901A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227839A (en) * | 1999-02-01 | 1999-09-08 | 天津大学 | Process for low-pressure synthesis of dimethyl carbonate by carbon monoxide |
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN101096340A (en) * | 2006-06-27 | 2008-01-02 | 上海焦化有限公司 | Process for the preparation of C1-C4-alkyl nitrites |
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945262A (en) * | 2014-03-28 | 2015-09-30 | 中国科学院大连化学物理研究所 | Method for preparing prepare methyl nitrite by catalyzing methanol to reduce dilute nitric acid |
| CN104945262B (en) * | 2014-03-28 | 2016-09-14 | 中国科学院大连化学物理研究所 | A kind of method of catalysis methanol reduction dust technology methyl nitrite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794321B (en) | Method for synthesizing aromatic carboxylic acid compounds in continuous flow microchannel reactor | |
| CN104761429B (en) | A kind of method for producing dimethyl carbonate and ethylene glycol | |
| CN104159880A (en) | Equilibrium direct synthesis of DME | |
| EP2697192A1 (en) | Method for preparation of ketoxime compound and method for preparation of alkoxy-amine hydrochloride | |
| CN102070575B (en) | New synthesis method of caronic anhydride | |
| CN101492370A (en) | Method for producing oxalic ester with CO coupling | |
| CN1793114B (en) | Process for producing cyclohexanone oxime | |
| CN113429267A (en) | Novel continuous process and device for preparing o-phenylphenol | |
| CN101125810A (en) | Method for preparing isooctanoic acid | |
| CN102442901A (en) | Method for producing dimethyloxalate | |
| CN103864587A (en) | Method for synthesizing 2-ethyl-2-hexenal | |
| CN101781217B (en) | Method for high-selectivity co-production of nitrocyclohexane and adipic acid | |
| CN106588657A (en) | Method for synthesizing dimethyl carbonate | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN106699696B (en) | A kind of co-production of propylene oxide and cyclohexanone | |
| CN112961030B (en) | Method for catalytic synthesis of 4- (trans-4-alkyl cyclohexyl) cyclohexanone | |
| CN101993363B (en) | Method for preparing oxalic ester by CO coupling | |
| CN106699695A (en) | Production method of propylene oxide | |
| CN102627526A (en) | Preparation method of 1,2-pentanediol | |
| CN101993374A (en) | Method for preparing C1-C4 alkyl nitrites | |
| CN102219679A (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN101993375A (en) | Method for producing C1-C4 alkyl nitrites | |
| CN112479858A (en) | Methanol carbonylation enhanced reaction system and process with aldehyde recovery function | |
| CN1090171C (en) | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation | |
| CN102442902A (en) | Method for producing dimethyloxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120509 |