CN1333086A - Catalyst for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation - Google Patents
Catalyst for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation Download PDFInfo
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- CN1333086A CN1333086A CN 00113091 CN00113091A CN1333086A CN 1333086 A CN1333086 A CN 1333086A CN 00113091 CN00113091 CN 00113091 CN 00113091 A CN00113091 A CN 00113091A CN 1333086 A CN1333086 A CN 1333086A
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Abstract
The present invention relates to a new-type catalyst for methyl alcohol liquid phase oxidation and oxonation to synthesize methyl carbonate. Said catalyst belongs to a complex of cuprous chloride and nitrogen-contained heterocyclic compound or polymer. In batch high-pressure still the methyl alcohol catalyst, CO and O2 are added, under the condition of 120-130 deg.C and 2.0-3.0 MPa the methyl carbonate can be synthesized, the per pass conversion of methyl alcohol is greater than or equal to 32%, and selectivity of target product is greater than or equal to 99.9%. Said invented catalyst is simple in preparation process, good in activity, selectivity and stability, and its service life is 1000 hr.
Description
The present invention relates to the cuprous chloride-nitrogen-containing heterocycle compound and the high-molecular complex as catalyst of synthesizing methyl carbonate by methanol liquid phase oxidation oxonation.
Methylcarbonate is a kind of Organic Chemicals with high added value, is widely used in the synthetic of performance resins, medicine, pesticide intermediate.The preparation method of methylcarbonate has phosgenation, ester-interchange method and methanol oxidation carbonyl process (comprising vapor phase process and liquid phase method).Wherein methanol solution phase oxidation carbonyl process has raw material and is easy to get, and technology is simple, low cost and other advantages.Italy Eni chem company is catalyzer with the cuprous chloride, and the technology of synthesizing methyl carbonate by methanol liquid phase oxidation oxonation has realized industrialization (Ind.Chim Ital, 21 (1), 1985).Cuprous chloride is corrosive to reaction unit, must add impregnating material such as glass lining at reactor wall, but this obstacle that has become device to maximize.In addition, in order to obtain enough speed of response, must use the cuprous chloride of high density in the Eni chem technology.Chinese patent CN1197792A (1998) is Primary Catalysts with CuCl, magnesium chloride, calcium chloride etc. are auxiliary agent, and the composite catalyst of preparation has improved the solvability of cuprous chloride in reaction solution, improved catalyst activity, but still do not had to solve etching problem equipment.
The heterogeneous ring compound and the polymer that the objective of the invention is with nitrogen atom are part, make catalyzer with the complex compound that cuprous chloride forms, and implement the reaction of synthesizing methyl carbonate by methanol liquid phase oxidation oxonation.Its characteristics be copper in the catalyzer/nitrogen mol ratio can be 1: 0.2～1: 5.0.Used nitrogen-containing heterocycle compound can be pyridine, imidazoles, multi-joint pyridine, aminopyridine, 4-phenylpyridine, N-Methyl pyrrolidone, polyvinyl pyridine, polyvinylpyrrolidone etc.This complex catalyst can improve the selectivity of conversion of methanol and methylcarbonate, and the corrodibility to reactor is very low simultaneously, can be without corrosion-proof lining.
The complex compound catalyst that cupric chloride that the present invention uses and nitrogen-containing heterocycle compound or nitrogen containing polymer form, be used for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation, reaction process condition suitable in the 250ml autoclave is: 100～140 ℃ of temperature, pressure 2.0～3.5MPa, methanol usage 50ml～100ml catalyst levels 1～10g, reaction times 10～60min, unstripped gas (CO+O
2) in oxygen level be 5～15%.The reaction product gas chromatographic analysis.Catalyst productivity is selectivity 〉=99.5% of 0.5g～3gDMC/g.cat.h. methylcarbonate.
Characteristics of the present invention are, the catalyst activity height, and the selectivity stability is good, and continuous operation is non-inactivation more than 1000 hours, and is not weightless.
Embodiment one
Add 50ml methyl alcohol in the 250ml autoclave, 2gCuCl-N-crassitude ketone catalyst (Cu/N=1) is with mixed gas (O
2: 8%, CO: the air in the metathesis reactor 92%), at room temperature use this gas pressurized to 3.0MPa then.120～130 ℃ of reactions 30 minutes.The cooling back is with gas chromatographic analysis.Methylcarbonate selectivity 99.9%, catalyst productivity 1.1 gDMC/g.cat.h.
Embodiment two
Make catalyzer (Cu/N=1) with 2gCuCl-aminopyridine complex compound.All the other conditions are with embodiment one, and the methylcarbonate selectivity is 99.5%, and catalyst productivity is 1.3gDMC/g.cat.h.
Embodiment three
With the mixture as catalyst (Cu/N=1.1) of 1gCuCl-pyridine complex (Cu/N=1) with 1gCuCl polyvinylpyrrolidone complex compound, all the other conditions are with embodiment one.The methylcarbonate selectivity is 99.6%, and catalyst productivity is 2.3gDMC/g.cat.h.
Embodiment four
With CuCl-polyvinyl pyridine alkane ketone is catalyzer, and (Cu/N=0.9) all the other conditions are with embodiment one.The methylcarbonate selectivity is 100%, and catalyst productivity is 1.5gDMC/g.cat.h.
Embodiment five
With the multi-joint pyridine of CuCl-is catalyzer (Cu/N=1.2), and all the other conditions are with embodiment one, and the methylcarbonate selectivity is 100%, and catalyst productivity is 2.8gDMC/g.cat.h.
Claims (4)
1. a CuCl complex compound catalyst that is used for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation is characterized in that part is nitrogen-containing heterocycle compound and nitrogen containing polymer.
2. described according to claim 1, it is characterized in that nitrogen-containing heterocycle compound and nitrogen containing polymer are pyridine, imidazoles aminopyridine, multi-joint pyridine (polymerization degree 2～10), 4-phenylpyridine, N-Methyl pyrrolidone, polyvinyl pyridine, polyvinylpyrrolidone etc.
3. described according to claim 1～2, it is characterized in that when part in the complex compound catalyst uses and can or use two kinds simultaneously with wherein a kind of.
4. described according to claim 1～3, it is characterized in that Cu/N element mol ratio is 1: 0.2～5.0 in the complex compound catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00113091 CN1114496C (en) | 2000-07-06 | 2000-07-06 | Catalyst for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation |
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| CN 00113091 CN1114496C (en) | 2000-07-06 | 2000-07-06 | Catalyst for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation |
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| CN1333086A true CN1333086A (en) | 2002-01-30 |
| CN1114496C CN1114496C (en) | 2003-07-16 |
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| CN 00113091 Expired - Lifetime CN1114496C (en) | 2000-07-06 | 2000-07-06 | Catalyst for synthesizing methyl carbonate by methanol liquid phase oxidation oxonation |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388978C (en) * | 2005-12-26 | 2008-05-21 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
| EP1947080A2 (en) | 2007-01-17 | 2008-07-23 | China Petrochemical Development Corporation | Process for preparation of dialkyl carbonate |
| EP2008990A1 (en) * | 2007-05-28 | 2008-12-31 | China Petrochemical Development Corporation | A method for preparing organic carbonates |
| CN100464853C (en) * | 2007-07-13 | 2009-03-04 | 浙江大学 | Carbon nitrogen coupling reaction catalyst composed of heterocycle functional group 1,3 diketone and halogenated univalence copper, and preparation method |
| CN101323572B (en) * | 2007-06-11 | 2011-09-14 | 中国石油化学工业开发股份有限公司 | Method for preparing dialkyl carbonates |
| CN101664697B (en) * | 2008-09-05 | 2013-01-23 | 中国石油化学工业开发股份有限公司 | Catalyst system for oxidative carbonylation and method for manufacturing dialkyl carbonate by using same |
| CN105080610A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院成都有机化学有限公司 | Process for preparing dimethyl carbonate catalyst by liquid-phase oxidation carbonylation of methanol |
| CN107175133A (en) * | 2017-05-10 | 2017-09-19 | 中国科学院福建物质结构研究所 | A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof |
| CN112439405A (en) * | 2020-12-21 | 2021-03-05 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof |
-
2000
- 2000-07-06 CN CN 00113091 patent/CN1114496C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388978C (en) * | 2005-12-26 | 2008-05-21 | 南京工业大学 | Complex catalyst for synthesizing carbonic ester by alcohol homogeneous oxidation carbonylation and preparation process and use method thereof |
| EP1947080A2 (en) | 2007-01-17 | 2008-07-23 | China Petrochemical Development Corporation | Process for preparation of dialkyl carbonate |
| EP1947080A3 (en) * | 2007-01-17 | 2008-09-10 | China Petrochemical Development Corporation | Process for preparation of dialkyl carbonate |
| US7700785B2 (en) | 2007-01-17 | 2010-04-20 | China Petrochemical Development Corporation | Process for preparation of dialkyl carbonate |
| EP2008990A1 (en) * | 2007-05-28 | 2008-12-31 | China Petrochemical Development Corporation | A method for preparing organic carbonates |
| CN101323572B (en) * | 2007-06-11 | 2011-09-14 | 中国石油化学工业开发股份有限公司 | Method for preparing dialkyl carbonates |
| CN100464853C (en) * | 2007-07-13 | 2009-03-04 | 浙江大学 | Carbon nitrogen coupling reaction catalyst composed of heterocycle functional group 1,3 diketone and halogenated univalence copper, and preparation method |
| CN101664697B (en) * | 2008-09-05 | 2013-01-23 | 中国石油化学工业开发股份有限公司 | Catalyst system for oxidative carbonylation and method for manufacturing dialkyl carbonate by using same |
| CN105080610A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院成都有机化学有限公司 | Process for preparing dimethyl carbonate catalyst by liquid-phase oxidation carbonylation of methanol |
| CN107175133A (en) * | 2017-05-10 | 2017-09-19 | 中国科学院福建物质结构研究所 | A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof |
| CN107175133B (en) * | 2017-05-10 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of silicon dioxide carried copper-dipyridyl catalyst and preparation method thereof |
| CN112439405A (en) * | 2020-12-21 | 2021-03-05 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof |
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|---|---|
| CN1114496C (en) | 2003-07-16 |
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Granted publication date: 20030716 |