CN102503817A - Photo-thermo concerted catalysis technology and application thereof on carbon monoxide catalytic coupling - Google Patents
Photo-thermo concerted catalysis technology and application thereof on carbon monoxide catalytic coupling Download PDFInfo
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- CN102503817A CN102503817A CN201110349697XA CN201110349697A CN102503817A CN 102503817 A CN102503817 A CN 102503817A CN 201110349697X A CN201110349697X A CN 201110349697XA CN 201110349697 A CN201110349697 A CN 201110349697A CN 102503817 A CN102503817 A CN 102503817A
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Abstract
The invention discloses photo-thermo concerted catalysis technology capable of improving carbon monoxide catalytic coupling performance, namely, sun light or an artificial light source is introduced into a thermo catalysis reaction device to improve multiple technical defects of the common carbon monoxide catalytic coupling reaction by the coaction of photocatalysis and thermo catalysis on a carbon monoxide catalytic coupling reaction system. According to the invention, the sun light or artificial light source is added on the basis of the original thermo catalysis reaction to affect a catalyst electron structure and the reactant adsorption state in a catalytic coupling process so as to generate photocatalysis-thermo catalysis synergism, thereby greatly reducing the optimal reaction temperature of the carbon monoxide catalytic coupling reaction and greatly improving the yields and selectivity of such target products as carbonate ester and oxalic ester, etc.
Description
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Technical field
The present invention relates to photochemical catalysis and the application of thermocatalysis coordination technique in catalyzed reaction, specifically hot concerted catalysis technology of Guang – and the application in the catalyzing carbon monoxide coupling thereof.
Background technology
Article are novel process and the new technologies that grow up the eighties in last century in the middle of the useful chemistry such as carbon monoxide gas-phase catalytic coupling synthesis of oxalic acid vinegar, carbonic ether; Being the important development direction of world today's C-1 chemistry industry, also is a great scientific and technological development project of China's C-1 chemistry industry.Abundant in conjunction with the coal resources in China reserves, and the deficient relatively present situation of petroleum resources, development is the feedstock production organic chemicals with the carbon monoxide, for alleviating the present oil pressure of China, the reasonable development coal resources have the important strategic meaning.
In recent years; Competitively carried out the research of carbon monoxide gas-phase catalytic synthesis of oxalate both at home and abroad; Company of Ube Industries Ltd. has succeeded in developing the novel process of carbon monoxide and nitrous acid ester atmospheric gas solid phase synthesis dimethyl oxalate like nineteen eighty-two, and to have carried out loaded catalyst be the pattern of 3kg; Chinese Academy of Sciences Chengdu organic in the period of 1985 – 1989, carried out the research of pure carbon monoxide gas phase catalysis synthesis of diethyl oxalate employing, studied five kinds of different catalyst systems; Chemical industry system of Zhejiang University also carried out the research of pure carbon monoxide gas phase catalysis synthesis of diethyl oxalate employing in 1989, and carried out the pilot scale of 200t/a synthesis of diethyl oxalate employing in the Jiangshan of Zhejiang Province chemical plant; Chinese Academy of Sciences's Fujian thing structure be domestic carry out carbon monoxide gas-phase catalytic synthesis of oxalic acid diester research reach one of successful unit the earliest; After nineteen eighty-two is developed highly active carbon monoxide gas-phase catalytic synthesis of oxalic acid two ester catalysts; Go through effort in more than 20 years; Accomplished the pilot scale of " carbon monoxide gas-phase catalytic synthesis of oxalate (300t/a) and terepthaloyl moietie (100t/a) " project in 2006; Reach the ability of 900 kilograms of dimethyl oxalates of daily output, and accomplished ton coal-ethylene glycol set technique technology, realized suitability for industrialized production in 2008; In addition, units such as domestic University Of Tianjin, East China University of Science, Nankai University have also carried out the research of carbon monoxide gas-phase catalytic synthesis of oxalate and terepthaloyl moietie in succession, but also do not have the successful report of pilot scale.Generally speaking; Although catalyzing carbon monoxide coupling producing oxalic ester has successfully been realized industriallization, also there is very big room for promotion from the angle of the energy, environment and economic benefit, such as; The optimal reaction temperature of mentioning in the above-mentioned research is generally more than 120oC; Temperature range also narrow (approximately 20oC) often contains by products such as methyl alcohol, methyl-formiate in the products obtained therefrom, catalyzer is generally palladium load aluminum oxide etc.
Summary of the invention
In order further to overcome the technical deficiency of conventional catalyzing carbon monoxide linked reaction; The present invention has introduced sunshine or source of artificial light on the basis of heat catalysis; The novel method of catalytic coupling carbon monoxide under a kind of Zai Guang – heat synergy is provided; Promptly through the acting in conjunction of photochemical catalysis and thermocatalysis, thereby effectively reduce temperature of reaction and improve the yield and the selectivity of product the carbon monoxide linked reaction.
Technical scheme of the present invention is following: in thermocatalysis; Make carbon monoxide generation linked reaction in conjunction with photocatalysis; Described thermocatalysis realizes through the heat catalysis device; Described heat catalysis device is made up of tubular reactor, granules of catalyst and heating system, and described photocatalysis realizes that through adding light source granules of catalyst places in the said tubular reactor; Heating system with add light source and place around the tubular reactor; Said heating system can be heating zone, oil bath, water-bath and process furnace, and said granules of catalyst is that palladium load aluminum oxide composite catalyst, particularly aluminum oxide and oxide semiconductor are (like TiO
2, ZnO, SnO
2, CeO
2, In
2O
3, Fe
2O
3Deng) material compound catalyzer, the said light source that adds is sunshine or source of artificial light, wavelength is 200-1200nm; The concrete grammar of the hot concerted catalysis coupling of light – carbon monoxide flows through described tubular reactor for the unstripped gas that will contain carbon monoxide and nitrous acid ester, and catalytic coupling becomes target products such as barkite or carbonic ether under certain reaction conditions.
The present invention combines photocatalysis technology and thermocatalysis technology exactly; In the heat catalysis device, introduce illumination; Through the synergy of photocatalysis and thermocatalysis, reduce the temperature of catalyzing carbon monoxide linked reaction and improve product yield and selectivity.
Effect of the present invention and meliority are: owing to introduced sunshine or source of artificial light at the heat catalysis device; They are through the influence to reaction species ADSORPTION STATE in catalyzer electronic structure and the catalytic coupling process; Produce Guang Cuiization – thermocatalysis synergy, thereby significantly reduced catalyzing carbon monoxide link coupled temperature of reaction and improved the selectivity of products such as dimethyl oxalate, oxalic acid diethyl ester, methylcarbonate, diethyl carbonate.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is described further.Fig. 1 is the skeleton diagram of the present invention's technology.In the heat catalysis device, introduce light source (comprising sunshine and source of artificial light), after the unstripped gas that contains carbon monoxide and nitrous acid ester flows through reactor drum, catalyzed coupling reaction takes place, generate target product.
Embodiment
Embodiment 1
Palladium carried titanium dioxide/aluminum oxide (Pd/TiO with immersion process for preparing
2/ Al
2O
3) be catalyzer; It is in the crystal reaction tube of 6mm that a certain amount of this catalyzer of 40 –, 60 orders is placed internal diameter, and the reaction tubes outside sandwich is through the recirculated water heating, and temperature of reaction is 70oC (positive and negative 1); In reaction tubes, feed the gas mixture (mol ratio is 14:12.5:73.5) of carbon monoxide, methyl nitrite and nitrogen; Gaseous tension is 0.1MPa, and gas flow is 30SCCM, and air speed is 70000h
-1, day island proper Tianjin GC-2014 type chromatographic instrument is used in the product on-line analysis.Experimental result is listed table 1 in.Can find out to have only under the heating condition, the reactionless and product-free generation of raw material.
Table 1
| Carbon monoxide transformation efficiency (%) | Dimethyl oxalate selectivity (%) | Oxalic acid diethyl ester selectivity (%) | Methylcarbonate selectivity (%) | Diethyl carbonate selectivity (%) |
| 0 | 0 | 0 | 0 | 0 |
Embodiment 2
Palladium carried titanium dioxide/aluminum oxide (Pd/TiO with immersion process for preparing
2/ Al
2O
3) be catalyzer, it is in the crystal reaction tube of 6mm that a certain amount of this catalyzer of 40 –, 60 orders is placed internal diameter, the reaction tubes outside sandwich is through the recirculated water heating; Temperature of reaction is 70oC (± 1), and the ultraviolet germicidal (Philips, predominant wavelength is 254nm) of 4 4W is surrounded on reaction tubes additional layer 2cm place; In reaction tubes, feed the gas mixture (mol ratio is 14:12.5:73.5) of carbon monoxide, methyl nitrite and nitrogen; Gaseous tension is 0.1MPa, and gas flow is 30SCCM, and air speed is 70000h
-1, day island proper Tianjin GC-2014 type chromatographic instrument is used in the product on-line analysis.Experimental result is listed table 2 in.Can find out that under the hot concerted catalysis effect of Zai Guang –, carbon monoxide and methyl nitrite can generate methylcarbonate by partial reaction, the carbon monoxide transformation efficiency is 10%, and the methylcarbonate selectivity is 100%.
Table 2
| Carbon monoxide transformation efficiency (%) | Dimethyl oxalate selectivity (%) | Oxalic acid diethyl ester selectivity (%) | Methylcarbonate selectivity (%) | Diethyl carbonate selectivity (%) |
| 10 | 0 | 0 | 100 | 0 |
Embodiment 3
Palladium carried titanium dioxide/aluminum oxide (Pd/TiO with immersion process for preparing
2/ Al
2O
3) be catalyzer, it is in the crystal reaction tube of 6mm that a certain amount of this catalyzer of 40 –, 60 orders is placed internal diameter, the reaction tubes outside sandwich heats through oil bath; Temperature of reaction is 90oC (positive and negative 1), and the ultraviolet germicidal (Philips, predominant wavelength is 254nm) of 4 4W is surrounded on reaction tubes additional layer 2cm place; In reaction tubes, feed the gas mixture (mol ratio is 14:12.5:73.5) of carbon monoxide, methyl nitrite and nitrogen; Gaseous tension is 0.1MPa, and gas flow is 30SCCM, and air speed is 70000h
-1, day island proper Tianjin GC-2014 type chromatographic instrument is used in the product on-line analysis.Experimental result is listed table 3 in.Can find out that under the hot concerted catalysis effect of Zai Guang –, carbon monoxide and methyl nitrite almost total overall reaction generate dimethyl oxalate, the carbon monoxide transformation efficiency reaches 95%, and the dimethyl oxalate selectivity is 100%.
Table 3
| Carbon monoxide transformation efficiency (%) | Dimethyl oxalate selectivity (%) | Oxalic acid diethyl ester selectivity (%) | Methylcarbonate selectivity (%) | Diethyl carbonate selectivity (%) |
| 95 | 100 | 0 | 0 | 0 |
Embodiment 4
Palladium carried titanium dioxide/aluminum oxide (Pd/TiO with immersion process for preparing
2/ Al
2O
3) be catalyzer, it is in the crystal reaction tube of 6mm that a certain amount of this catalyzer of 40 –, 60 orders is placed internal diameter, reaction tubes is simultaneously through the heating zone heating; Temperature of reaction is 80oC (± 1); The xenon lamp of a 300W is placed at reaction tubes another side 2cm place, in reaction tubes, feeds the gas mixture (mol ratio is 14:12.5:73.5) of carbon monoxide, methyl nitrite and nitrogen, and gaseous tension is 0.1MPa; Gas flow is 30SCCM, and air speed is 70000h
-1, day island proper Tianjin GC-2014 type chromatographic instrument is used in the product on-line analysis.Experimental result is listed table 4 in.Can find out that under the hot concerted catalysis effect of Zai Guang –, carbon monoxide and methyl nitrite can react and generate dimethyl oxalate and methylcarbonate, the carbon monoxide transformation efficiency reaches 80%, and the dimethyl oxalate selectivity is 80%, and the methylcarbonate selectivity is 20%.
Table 4
| Carbon monoxide transformation efficiency (%) | Dimethyl oxalate selectivity (%) | Oxalic acid diethyl ester selectivity (%) | Methylcarbonate selectivity (%) | Diethyl carbonate selectivity (%) |
| 80 | 80 | 0 | 20 | 0 |
Claims (7)
1. method through light heat synergetic action catalytic coupling carbon monoxide; It is characterized in that: in thermocatalysis; Make carbon monoxide generation linked reaction in conjunction with photocatalysis, described thermocatalysis realizes that through the heat catalysis device described heat catalysis device is made up of tubular reactor, granules of catalyst and heating system; Described photocatalysis realizes through adding light source; Granules of catalyst places in the said tubular reactor, heating system with add light source and place around the tubular reactor, the said light source that adds is sunshine or source of artificial light; The concrete grammar of photo-thermal concerted catalysis coupling carbon monoxide flows through described tubular reactor for the unstripped gas that will contain carbon monoxide, and catalytic coupling becomes target product under certain reaction conditions.
2. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1 is characterized in that described granules of catalyst can be palladium catalyst for titanium dioxide loaded Pd/TiO
2, palladium load Zinc oxide catalytic Pd/ZnO, palladium carried titanium dioxide/aluminium oxide catalyst Pd/TiO
2/ Al
2O
3, palladium load zinc oxide/alumina catalyst P d/ZnO/Al
2O
3Deng.
3. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1 is characterized in that described source of artificial light is ultraviolet germicidal or xenon lamp, and illumination wavelength is 200 ~ 1200nm.
4. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1 is characterized in that described heating system can be the heating zone, oil bath, water-bath, process furnace etc.
5. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1; It is characterized in that described unstripped gas is the gas mixture of carbon monoxide, nitrous acid ester and nitrogen; Gas is formed in molar percentage; Be controlled to be an oxygen carbon – 5 ~ 17%, inferior nitric ether – 5.5 ~ 15%, all the other are nitrogen.
6. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1 is characterized in that described reaction conditions does, temperature of reaction 20 ~ 140oC, pressure 0.1 ~ 0.5MPa, flow 10 ~ 50SCCM.
7. the method through light heat synergetic action catalytic coupling carbon monoxide according to claim 1 is characterized in that described target product is a dimethyl oxalate, oxalic acid diethyl ester, methylcarbonate, one or more in the diethyl carbonate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN108261985A (en) * | 2018-01-17 | 2018-07-10 | 天津中环电炉股份有限公司 | A kind of horizontal-type high temperature photo-thermal catalytic reaction device |
| CN108404819A (en) * | 2018-04-19 | 2018-08-17 | 中国科学院理化技术研究所 | Photo-thermal synergetic gas-solid phase catalytic reaction device and application thereof |
| CN108982621A (en) * | 2018-09-21 | 2018-12-11 | 京东方科技集团股份有限公司 | A kind of pollutant testing apparatus, wearable device |
| CN111229218A (en) * | 2020-01-10 | 2020-06-05 | 清华大学 | Monoatomic palladium composite catalyst and preparation method and application thereof |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN104923225B (en) * | 2014-03-18 | 2018-12-21 | 中国科学院大连化学物理研究所 | A kind of loaded noble metal catalyst and its preparation and application |
| CN108261985A (en) * | 2018-01-17 | 2018-07-10 | 天津中环电炉股份有限公司 | A kind of horizontal-type high temperature photo-thermal catalytic reaction device |
| CN108404819A (en) * | 2018-04-19 | 2018-08-17 | 中国科学院理化技术研究所 | Photo-thermal synergetic gas-solid phase catalytic reaction device and application thereof |
| CN108982621A (en) * | 2018-09-21 | 2018-12-11 | 京东方科技集团股份有限公司 | A kind of pollutant testing apparatus, wearable device |
| CN111229218A (en) * | 2020-01-10 | 2020-06-05 | 清华大学 | Monoatomic palladium composite catalyst and preparation method and application thereof |
| CN111229218B (en) * | 2020-01-10 | 2021-01-01 | 清华大学 | Monoatomic palladium composite catalyst and preparation method and application thereof |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
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Application publication date: 20120620 |