CN104307546A - Transition metal catalyst with Pt-group metal dotted active points - Google Patents
Transition metal catalyst with Pt-group metal dotted active points Download PDFInfo
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- CN104307546A CN104307546A CN201410604590.9A CN201410604590A CN104307546A CN 104307546 A CN104307546 A CN 104307546A CN 201410604590 A CN201410604590 A CN 201410604590A CN 104307546 A CN104307546 A CN 104307546A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a transition metal catalyst with Pt-group metal dotted active points. The transition metal catalyst adopts a layer structure, wherein the inner layer is a carrier including Al2O3, MgO, SiO2, TiO2, ZrO2, foamed ceramic, rare-earth oxide and composite oxide; the middle layer is a WC layer; the outer layer is a Pt-group metal layer including a Pt metal layer, a Pd metal layer, an Rh metal layer, an Ru metal layer and a Ir metal layer; the WC layer is continuous dense coating with the thickness of 0.1-2 microns; the Pt-group metal layer, with the thickness of 0.01-10 microns, is incontinuous and adopts a mesoporous structure with the mesopore diameter being 100-1000 nm. The catalyst has a larger specific surface area, and metal particles and the mesopores are in strong and mutual action, so that generation of carbon is prevented, and stability of the catalyst is kept; meanwhile, a synergistic effect is realized in duplex metal, so that in the methane-carbon dioxide catalytic reforming reaction, the catalyst has excellent catalytic activity and carbon deposit resistance performance, which can obviously improve the reaction efficiency.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to the transition-metal catalyst that a kind of Pt race metal intersperses active site.
Background technology
Methane is the main component of natural gas, day by day exhausted along with petroleum resources, and the natural gas resource of rich reserves will become one of alternative energy source that most wishes.In the face of huge resources advantage, natural gas utilize level also very low.Therefore, natural gas is converted into the chemical products being easy to liquid fuel or the high added value of transporting by means such as chemical catalysis, by researcher numerous in world wide is paid close attention to.Methane molecule has similar inert gas electronic configuration, molecular structure that stereochemical structure is very symmetrical, and c h bond can up to 435kJ/mol, thermodynamically highly stable.How to make molecule stable like this obtain effective activation, and then realize rationally transforming, become one of problem the most challenging in current heterogeneous catalysis field.In general, methane synthesis gas has three approach: i.e. steam reforming, methane portion oxidation and CO 2 reformation.Wherein CO 2 reformation synthetic gas production process tool has the following advantages: H in the synthesis gas that (1) produces
2/ CO ratio is about 1, can directly as the raw material of carbonylation synthesis, compensate for the deficiency that in the synthesis gas that steam reforming obtains, C/Hratio is higher; (2) make use of methane and carbon dioxide these two kinds simultaneously and maximum gas is endangered to the earth, improve the ecological environment of the mankind; (3) methane-CO 2 reformation is the reversible reaction with larger reaction heat, can as the medium of energy storage.This process is a strong endothermic reaction (⊿ H=248 kJ/mo l), need higher reaction temperature (800 DEG C).Therefore, development high activity, height are selected and the catalyst of high stable is one of methyl hydride catalyzed reformation key factor realizing commercial Application, are also the focuses in this area research.
Carried noble metal (Pt, Pd, Rh, Ru and Ir) catalyst shows very high activity, selective and coking resistivity in methane reforming with carbon dioxide, except V
outside group 4 transition metal, some researchers also find that the sulfide of Mo, W and the oxide of carbide and Mn all have good reactivity and coking resistivity, except employing monometallic is except active component, if take bimetallic as active component, owing to producing certain synergy between bimetallic, can obtain an effect of mutually promoting, therefore bimetallic catalyst have more superior catalytic activity and coking resistivity.In the eurypalynous catalyst of crowd, meso-hole structure catalyst has larger specific area and pore volume, and the features such as good anti-carbon deposit and anti-agglutinatting property, development in recent years is rapid.(400 DEG C) three kinds of different structures (nanometer, mesoporous and macroporous structure) La under having researcher to have studied low temperature
2o
3– ZrO
2stability, result shows, the Ni/La of meso-hole structure
2o
3– ZrO
2stability best, almost unchanged after reaction 180h, and another two kinds of its activity decrease about 20% when 100h.The main cause of nanometer and macroporous structure catalysqt deactivation is that the generation of catalyst surface carbon and Ni particulate are by NiO
xparcel; And meso-hole structure catalyst has larger specific area and pore volume, NiOx wherein can make the Interaction enhanced between Ni particulate and meso-hole structure carrier, prevent the generation of carbon and Ni particulate oxidized, maintain its stability.Current catalyst structure more options carrier structure is meso-hole structure, and consumption is relatively large, but selects load to be that the catalyst of meso-hole structure is also rarely found.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, a kind of Pt race metal is provided to intersperse the transition-metal catalyst of active site, the Pt race metal on surface is discontinuous, there is meso-hole structure, increase the specific area of catalyst, the synergy between bimetallic can be given full play to again simultaneously, there is very superior catalytic activity and coking resistivity in methane and carbon dioxide catalytic reforming reaction, improve the efficiency of reaction.
Pt race metal intersperses a transition-metal catalyst for active site, it is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and skin is Pt race metal level, comprises Pt, Pd, Rh, Ru, Ir metal level; Described carrier is Al
2o
3, MgO, SiO
2, TiO
2, ZrO
2, foamed ceramics, rare-earth oxide, composite oxides; Described WC layer thickness is 0.1 ~ 2 μm, is the continuous coated of densification; The thickness of Pt race metal level is 0.01 ~ 10 μm, and the Pt race metal on surface is discontinuous, and have meso-hole structure, aperture is 100nm ~ 1000nm.
Advantage of the present invention: (1) load Zhong You Pt race's metal level and WC coating two-layer, the synergy between bimetallic can be given full play to.(2) surface Pt race metal level there is meso-hole structure, the specific area and the hole that drastically increase catalyst are amassed, metal particle and mesoporous between Interaction enhanced, prevent the generation of carbon, maintain stability and the catalytic activity of catalyst.(3) Pt race metal, comprises Pt, Pd, Rh, Ru and Ir, comparatively rare, thus expensive, and discontinuous structure is selected on surface, has saved the cost of manufacture of catalyst to a certain extent.
Detailed description of the invention
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims and limited.
embodiment 1
Pt race metal intersperses a transition-metal catalyst for active site, it is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and skin is Pt metal level, and carrier is Al
2o
3; Wherein WC layer thickness is 0.5 μm, is the continuous coated of densification; The thickness of Pt metal level is 0.5 μm, and the Pt metal on surface is discontinuous, and have meso-hole structure, aperture is 200nm.This catalyst has larger specific area, metal particle and mesoporous between Interaction enhanced, prevent the generation of carbon, maintain the stability of catalyst, simultaneously, synergy between bimetallic is given full play to, and thus in methane and carbon dioxide catalytic reforming reaction, this catalyst has very superior catalytic activity and coking resistivity, can significantly improve the efficiency of reaction.
embodiment 2
Pt race metal intersperses a transition-metal catalyst for active site, it is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and skin is Rh race metal level, and carrier is SiO
2; Wherein WC layer thickness is 2 μm, is the continuous coated of densification; The thickness of Rh metal level is 10 μm, and the Rh metal on surface is discontinuous, and have meso-hole structure, aperture is 1000nm.This catalyst has larger specific area, metal particle and mesoporous between Interaction enhanced, prevent the generation of carbon, maintain the stability of catalyst, simultaneously, synergy between bimetallic is given full play to, and thus in methane and carbon dioxide catalytic reforming reaction, this catalyst has very superior catalytic activity and coking resistivity, can significantly improve the efficiency of reaction.
Above are only two detailed description of the invention of the present invention, but design concept of the present invention is not limited thereto, all changes utilizing this design the present invention to be carried out to unsubstantiality, all should belong to the behavior of invading the scope of protection of the invention.In every case be the content not departing from technical solution of the present invention, any type of simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (4)
1. Pt race metal intersperses a transition-metal catalyst for active site, it is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and skin is Pt race metal level, comprises Pt, Pd, Rh, Ru, Ir metal level.
2. catalyst according to claim 1, is characterized in that described carrier is Al
2o
3, MgO, SiO
2, TiO
2, ZrO
2, foamed ceramics, rare-earth oxide, composite oxides.
3. catalyst according to claim 1, is characterized in that described WC layer thickness is 0.1 ~ 2 μm, is the continuous coated of densification.
4. catalyst according to claim 1, it is characterized in that surperficial Pt race metal level is discontinuous, thickness is 0.01 ~ 10 μm, has meso-hole structure, and aperture is 100nm ~ 1000nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604590.9A CN104307546A (en) | 2014-11-03 | 2014-11-03 | Transition metal catalyst with Pt-group metal dotted active points |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604590.9A CN104307546A (en) | 2014-11-03 | 2014-11-03 | Transition metal catalyst with Pt-group metal dotted active points |
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| Publication Number | Publication Date |
|---|---|
| CN104307546A true CN104307546A (en) | 2015-01-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003117398A (en) * | 2001-10-12 | 2003-04-22 | Toyota Motor Corp | Wc carrying catalyst and production method thereof |
| CN101801841A (en) * | 2007-04-27 | 2010-08-11 | 市川胜 | Supported catalyst for hydrogenation/dehydrogenation reaction, method for production of the catalyst, and hydrogen storage/supply method using the catalyst |
| CN103506144A (en) * | 2012-06-27 | 2014-01-15 | 浙江工业大学 | Tungsten carbide/platinum composite material with core-shell structure as well as preparation and application thereof |
-
2014
- 2014-11-03 CN CN201410604590.9A patent/CN104307546A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003117398A (en) * | 2001-10-12 | 2003-04-22 | Toyota Motor Corp | Wc carrying catalyst and production method thereof |
| CN101801841A (en) * | 2007-04-27 | 2010-08-11 | 市川胜 | Supported catalyst for hydrogenation/dehydrogenation reaction, method for production of the catalyst, and hydrogen storage/supply method using the catalyst |
| CN103506144A (en) * | 2012-06-27 | 2014-01-15 | 浙江工业大学 | Tungsten carbide/platinum composite material with core-shell structure as well as preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 齐增新等: ""核壳结构C@WC 载体的制备及Pd /C@WC催化剂对甲酸的电催化氧化"", 《应用化学》 * |
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Application publication date: 20150128 |
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