CN103495416A - Carbon-material supported catalyst for acetylene hydrochlorinate reaction - Google Patents
Carbon-material supported catalyst for acetylene hydrochlorinate reaction Download PDFInfo
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- CN103495416A CN103495416A CN201310504289.6A CN201310504289A CN103495416A CN 103495416 A CN103495416 A CN 103495416A CN 201310504289 A CN201310504289 A CN 201310504289A CN 103495416 A CN103495416 A CN 103495416A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 title abstract description 22
- 239000003575 carbonaceous material Substances 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 5
- 239000004917 carbon fiber Substances 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 1
- 239000002041 carbon nanotube Substances 0.000 abstract 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 150000001345 alkine derivatives Chemical class 0.000 description 6
- 150000002940 palladium Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002525 ultrasonication Methods 0.000 description 5
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a carbon-material supported catalyst for an acetylene hydrochlorinate reaction. The catalyst mainly comprises active components and a supporter, the active components of the catalyst are palladium chloride, the loading capacity of the active components is 0.01-15wt%, and the supporter of the catalyst is one of a carbon nano tube, carbon fibers, graphene and other carbon materials. The supporters of the catalyst is prepared by adopting an in-situ chemical oxidative polymerization pretreatment method and a soaking method, and the activity of the catalyst is evaluated and tested under the condition that the feed gas space speed is 120h-1, the feed gas proportion is that V(HC1):V(C2H2)=1-2, pressure is normal, and reaction temperature is 100-200 DEG C. The carbon-material supported catalyst has the advantages that the prepared catalyst is environmentally friendly, the components of the catalyst are simple and stable, and the catalytic activity is high; the conversion percent of acetylene is larger than 96%, and the selectivity of chloroethylene can reach more than 99%.
Description
Technical field
The present invention relates to a kind of support type catalyst without mercury that can be used for the acetylene hydrochlorination reaction and preparation method thereof and application, belonged to catalyst preparation technology and application in organic synthesis.
Background technology
Acetylene hydrochlorination is the important chemical reaction of synthesizing chloroethylene (VCM) monomer.Vinyl chloride is the important monomer of synthesizing polyvinyl chloride (PVC).As one of the world's five large-engineering materials, polyvinyl chloride is used widely at industry, agricultural, building, daily life field, and demand is large in the world.
The industrial production of VCM mainly contains at present: acetylene method and ethylene process.Ethylene process belongs to the petrochemical industry route, and due to the national conditions of oil-poor rich coal, acetylene method is occupied an leading position in the production of VC in China monomer.This method be take coal as raw material, through calcium carbide, arrives acetylene, then reaction obtains VCM through acetylene hydrochlorination.At present, the HgCl adopted due to the acetylene hydrochlorination reaction
2/ activated-carbon catalyst causes negative effect to environment, and mercury scarcity of resources in global range, makes acetylene method face immense pressure.Studied for improvement and the substitute of mercury chloride for a long time both at home and abroad, but still be there is no great breakthrough so far.Therefore finding the environment-friendly type catalyst without mercury replaces mercuric chleride catalyst and seems particularly important.
Report about the research of acetylene hydrochlorination reaction catalyst without mercury mainly concentrates on active component both at home and abroad.Comprise noble metal and base metal.Catalyst is carrier mainly with active carbon greatly, Chinese invention patent application numbers 201310106438.3 discloses a kind of preparation method and application of novel nitrogen modification cocoanut active charcoal, active carbon with urea, ammoniacal liquor, the modification of melamine coconut husk, Au is active component, adopts equi-volume impregnating to prepare catalyst.Document [Li Xiaoyan, Zhu Mingyuan, Dai Bin. Aucl
3on polypyrrole-modified carbon nanotubes as acetylene hydrochlorination catalysts[J]. Applied Catalysis B:Environmental, 2013,142-143:234-240] reported and usingd noble metal Au as active component, the catalyst that CNT is carrier, in addition in open source literature and patent, there is not yet material with carbon element is that carrier, noble metal and base metal are active component and add the further research of auxiliary agent for the acetylene hydrochlorination reaction.
The present invention proposes a kind of carbon material supported type novel mercury-free catalyst that can be used for the acetylene hydrochlorination reaction.It is significant to acetylene hydrochlorination reaction production vinyl chloride.
Summary of the invention
The objective of the invention is harm and mercury scarcity of resources problem to environment for the mercuric chleride catalyst of acetylene hydrochlorination reaction, be provided for preparing vinyl chloride by hydrochlorination of acetylene support type catalyst without mercury and preparation method thereof.
The active component of catalyst provided by the invention is palladium salt, and the load capacity of active component is 0.01-15wt%, and the carrier of catalyst comprises the wherein a kind of of the material with carbon elements such as CNT, carbon fiber, Graphene.
The present invention realizes by following technical measures, and detailed process is as follows:
1, the preparation of carbon material supported type catalyst
Ultrasonic-in situ chemical oxidative polymerization infusion process preparation that catalyst provided by the invention is taked.
Detailed process is: be dissolved into after quantitative palladium bichloride is wetting with distilled water in appropriate acid, be made into certain density palladium salt maceration extract.Get above-mentioned solution impregnation on pretreatment material with carbon element carrier, by ultrasonic or rotary evaporation dipping, drying.
Catalyst activity evaluation is carried out in fixed bed reactors (quartz glass material).At unstripped gas air speed 120 h
-1, the unstripped gas ratio is V (HCl): V (C
2h
2)=1 ~ 2, normal pressure, carry out the acetylene hydrochlorination reaction test to this catalyst under 100 ~ 200 ℃ of conditions of reaction temperature, and reaction end gas is processed by the gas-chromatography sample analysis and is calculated conversion of alkyne and ethylene selectivity with alkali lye.Institute's controlling catalyst conversion of alkyne is greater than 96%, selectively can the reaching more than 99% of vinyl chloride.
The invention has the advantages that: material with carbon element carrier pretreatment unit is simple, easy and simple to handle, catalyst environment close friend, and activity component load quantity is little, and catalytic performance is good.
The specific embodiment:
Embodiment 1:
Take Graphene dry after certain processing, quantitative palladium salt maceration extract and alkali metal (as Na, K, Al etc.) auxiliary agent are impregnated on above-mentioned Graphene, with ultrasonic or rotary evaporation impregnation drying, the load capacity of the tenor in the gained catalyst on carrier is 0.01-4wt%.
Above-mentioned catalyst is packed in fixed bed reactors (quartz glass material).At unstripped gas air speed 120 h
-1, the unstripped gas ratio is V (HCl): V (C
2h
2)=1.2:1, normal pressure, carry out the test of acetylene hydrochlorination reactivity to this catalyst under 180 ℃ of conditions of reaction temperature, analytical reactions tail gas, the conversion of alkyne of catalyst is 96.25%, vinyl chloride is selectively 99.33%.
Embodiment 2:
Take carbon fiber dry after certain processing, quantitative palladium salt maceration extract and alkaline-earth metal (as Be, Mg, Ba etc.) auxiliary agent are impregnated on above-mentioned CNT, with ultrasonic or rotary evaporation impregnation drying, the load capacity of the tenor in this catalyst on carrier is 4-8wt%.
Above-mentioned catalyst is packed in fixed bed reactors (quartz glass material).At unstripped gas air speed 120 h
-1, the unstripped gas ratio is V (HCl): V (C
2h
2)=1.2:1, normal pressure, carry out the test of acetylene hydrochlorination reactivity to this catalyst under 180 ℃ of conditions of reaction temperature, analytical reactions tail gas, the conversion of alkyne of catalyst is 97.32%, vinyl chloride is selectively 99.57%.
Embodiment 3:
Take CNT dry after certain processing, quantitative palladium salt maceration extract and rare earth metal (as La, Ce, Lu etc.) auxiliary agent are impregnated on above-mentioned CNT, with ultrasonic or rotary evaporation impregnation drying, the load capacity of the tenor in this catalyst on carrier is 8-12wt%.
Above-mentioned catalyst is packed in fixed bed reactors (quartz glass material).At unstripped gas air speed 120 h
-1, the unstripped gas ratio is V (HCl): V (C
2h
2)=1.2:1, normal pressure, carry out the test of acetylene hydrochlorination reactivity to this catalyst under 180 ℃ of conditions of reaction temperature, analytical reactions tail gas, the conversion of alkyne of catalyst is 96.51%, vinyl chloride is selectively 99.28%.
Embodiment 4:
Take carbon fiber dry after certain processing, quantitative palladium salt maceration extract and transition metal (as Fe, Cu, Mn etc.) auxiliary agent are impregnated on above-mentioned CNT, with ultrasonic or rotary evaporation impregnation drying.The load capacity of tenor in this catalyst on carrier is 12-15wt%.
Above-mentioned catalyst is packed in fixed bed reactors (quartz glass material).At unstripped gas air speed 120 h
-1, the unstripped gas ratio is V (HCl): V (C
2h
2)=1.2:1, normal pressure, carry out the test of acetylene hydrochlorination reactivity to this catalyst under 180 ℃ of conditions of reaction temperature, analytical reactions tail gas, the conversion of alkyne of catalyst is 97.51%, vinyl chloride is selectively 99.15%.
Claims (5)
1. one kind can be used for the support type catalyst without mercury that acetylene hydrochlorination reacts.
2. catalyst according to claim 1 is characterized in that catalyst comprises active component and material with carbon element carrier.
3. catalyst according to claim 1, is characterized in that active component is palladium salt, and active component is 0.01-15wt% in the load capacity of material with carbon element carrier.
4. catalyst according to claim 1, is characterized in that carrier selected the wherein a kind of of the material with carbon elements such as CNT, carbon fiber, Graphene.
5. according to claim 1,2,3 and 4 described catalyst, it is characterized in that having added alkali metal (as Na, K, Al etc.), alkaline-earth metal (as Be, Mg, Ba etc.), rare earth metal (as La, Ce, Lu etc.), transition metal (as Fe, Cu, Mn etc.) Four types auxiliary agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310504289.6A CN103495416A (en) | 2013-10-24 | 2013-10-24 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310504289.6A CN103495416A (en) | 2013-10-24 | 2013-10-24 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103495416A true CN103495416A (en) | 2014-01-08 |
Family
ID=49860728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310504289.6A Pending CN103495416A (en) | 2013-10-24 | 2013-10-24 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
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|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289603A (en) * | 2014-12-02 | 2016-02-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing high-dispersibility gold-loading catalyst |
| CN106944110A (en) * | 2017-04-28 | 2017-07-14 | 武汉工程大学 | A kind of hydrogen chloride synthesis vinyl chloride thereof catalyst without mercury and preparation method |
| CN107803213A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of stable palladium compound of acetylene atmosphere high temperature and its application |
| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN109746012A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination reaction structure catalyst and preparation and application based on fine and close pipe wall hollow foamed material |
| CN109745971A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | A kind of structural catalyst and its application based on hollow foam material |
| CN111330585A (en) * | 2020-03-23 | 2020-06-26 | 鄂尔多斯市瀚博科技有限公司 | Preparation method and application of modified catalyst |
| CN111744510A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Carbon nano tube mercury-free catalyst for acetylene hydrochlorination |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380380A (en) * | 2011-09-02 | 2012-03-21 | 新疆大学 | Mercury-free catalyst system for acetylene hydrochlorination and use thereof |
-
2013
- 2013-10-24 CN CN201310504289.6A patent/CN103495416A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380380A (en) * | 2011-09-02 | 2012-03-21 | 新疆大学 | Mercury-free catalyst system for acetylene hydrochlorination and use thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289603A (en) * | 2014-12-02 | 2016-02-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing high-dispersibility gold-loading catalyst |
| CN106944110A (en) * | 2017-04-28 | 2017-07-14 | 武汉工程大学 | A kind of hydrogen chloride synthesis vinyl chloride thereof catalyst without mercury and preparation method |
| CN107803213A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of stable palladium compound of acetylene atmosphere high temperature and its application |
| CN107803213B (en) * | 2017-09-29 | 2020-04-24 | 浙江工业大学 | Palladium compound with high-temperature stability in acetylene atmosphere and application thereof |
| CN109746012A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination reaction structure catalyst and preparation and application based on fine and close pipe wall hollow foamed material |
| CN109745971A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | A kind of structural catalyst and its application based on hollow foam material |
| CN109746012B (en) * | 2017-11-08 | 2022-01-14 | 中国科学院金属研究所 | Acetylene hydrochlorination structured catalyst based on compact pipe wall hollow foam material, and preparation and application thereof |
| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN111744510A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Carbon nano tube mercury-free catalyst for acetylene hydrochlorination |
| CN111330585A (en) * | 2020-03-23 | 2020-06-26 | 鄂尔多斯市瀚博科技有限公司 | Preparation method and application of modified catalyst |
| CN111330585B (en) * | 2020-03-23 | 2023-04-18 | 鄂尔多斯市瀚博科技有限公司 | Preparation method and application of modified catalyst |
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Application publication date: 20140108 |