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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- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 53
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 25
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 23
- 238000010168 coupling process Methods 0.000 title claims abstract description 20
- 230000008878 coupling Effects 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 238000005516 engineering process Methods 0.000 title abstract description 10
- 230000002153 concerted effect Effects 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 230000002070 germicidal effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims 4
- 239000002245 particle Substances 0.000 claims 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 150000003901 oxalic acid esters Chemical class 0.000 abstract 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- -1 nitrous acid ester Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
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Abstract
本发明公布了一种能够改善一氧化碳催化偶联性能的光–热协同催化技术，即在热催化反应装置中引入太阳光或人工光源，通过光催化和热催化对一氧化碳催化偶联反应体系的共同作用，从而改善了常规一氧化碳催化偶联反应的一些技术性不足。本发明由于在原有热催化反应作用的基础上外加了太阳光或人工光源，通过对催化剂电子结构和催化偶联过程中反应物种吸附态的影响，产生光催化–热催化协同作用，使得一氧化碳催化偶联反应的最佳反应温度明显降低，同时碳酸脂、草酸酯等目标产品的收率和选择性也显著提高。
The invention discloses a photo-thermal synergistic catalysis technology capable of improving the catalytic coupling performance of carbon monoxide, that is, introducing sunlight or artificial light into the thermal catalytic reaction device, and synergistically synergizing the catalytic coupling reaction system of carbon monoxide through photocatalysis and thermal catalysis. Effect, thereby improving some technical deficiencies of the conventional carbon monoxide catalyzed coupling reaction. Due to the addition of sunlight or artificial light source on the basis of the original thermocatalytic reaction, the present invention produces photocatalysis-thermocatalysis synergistic effect through the influence on the electronic structure of the catalyst and the adsorption state of the reaction species in the catalytic coupling process, so that carbon monoxide catalyzes The optimal reaction temperature of the coupling reaction is significantly reduced, and the yield and selectivity of target products such as carbonate esters and oxalic acid esters are also significantly improved.
Description
?
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 |
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|---|---|---|---|
| CN201110057193 | 2011-03-10 | ||
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| CN201110349697XA CN102503817A (en) | 2011-03-10 | 2011-11-08 | Photo-thermo concerted catalysis technology and application thereof on carbon monoxide catalytic coupling |
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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 | A kind of single-atom palladium composite catalyst and its preparation method and use |
| 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 |