CN104307547A - Pt-ZrO2/WC (Wolfram Carbide) catalyst in methane-carbon dioxide catalytic reforming reaction - Google Patents

Pt-ZrO2/WC (Wolfram Carbide) catalyst in methane-carbon dioxide catalytic reforming reaction Download PDF

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CN104307547A
CN104307547A CN201410604642.2A CN201410604642A CN104307547A CN 104307547 A CN104307547 A CN 104307547A CN 201410604642 A CN201410604642 A CN 201410604642A CN 104307547 A CN104307547 A CN 104307547A
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CN104307547B (en
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沙李丽
聂丽丽
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Taicang Paiou Technology Consulting Service Co Ltd
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Abstract

The invention provides a Pt-ZrO2/WC catalyst in a methane-carbon dioxide catalytic reforming reaction. The Pt-ZrO2/WC catalyst is of a stratified structure with a carrier in the inner layer and comprises Al2O3, MgO, SiO2, TiO2, ZrO2, foamed ceramic, rare-earth oxide, composite oxide or a carbon/carbon composite material, wherein the interlayer serves as the WC layer; the outermost layer serves as the Pt-ZrO2 layer; the WC layer is 0.5-10 microns thick; the Pt-ZrO2 layer is 0.01-1 micron thick; the Pt metal at the outermost layer is discontinuous and provided with a mesoporous structure; the pore diameter is 2-50 nm; Pt accounts for 20-50% of the Pt-ZrO2 layer, Zr elementary substance and the Zr alloy account for 10-20% of the Pt-ZrO2 layer, and ZrO2 accounts for 30-40% of the Pt-ZrO2 layer; the outermost layer comprises Pt3Zr, PtZr and Pt3Zr5 compounds. The catalyst is larger in specific surface area, the interaction between the metal particles and the mesopores is enhanced to prevent generation of carbon, so that the stability of the catalyst is maintained, and meanwhile the synergistic effect of the duplex metal is fully expressed, so that the catalyst is very excellent in catalytic activity and carbon deposit resistance, and further the reaction efficiency is obviously improved.

Description

Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst
Technical field
The present invention relates to a kind of catalyst, particularly relate to the Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst.
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 system of methane and carbon dioxide catalytic reforming producing synthesis gas, common carbon deposit has thread charcoal, polymer charcoal and graphite charcoal.Carbon distribution problem hinders one of its key issue moving towards practical application, has researcher at 853 K, VCO 2: VCH 4under=1:1 condition, investigate Pt/ZrO 2reforming catalyst.After continuous operation 500 h, carry out TGA/DSC to catalyst and analyze, result shows catalyst generates without carbon deposit.Think that carbon is at Pt/ZrO 2dissolubility on catalyst is little.This is because Pt has stronger electron supplying capacity, methane molecule is inhibit to dissociate at catalyst surface in catalyst surface cracking and acceleration carbon dioxide molecule.
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, provides the Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst, outermost layer is Pt-ZrO 2alloy-layer, has given full play to the synergy between bimetallic, has very superior catalytic activity and coking resistivity in methane and carbon dioxide catalytic reforming reaction.In addition, the Pt on surface is discontinuous, has meso-hole structure, increases the specific area of catalyst, prevent the generation of carbon and metal particle oxidized, thus improve reaction efficiency.
Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst, is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and outermost layer is Pt-ZrO 2layer; Described carrier is Al 2o 3, MgO, SiO 2, TiO 2, ZrO 2, foamed ceramics, rare-earth oxide, composite oxides or carbon/carbon compound material; Described WC layer thickness is 0.5 ~ 10 μm, Pt-ZrO 2layer thickness is 0.01 ~ 1 μm; Described outermost Pt metal is discontinuous, has meso-hole structure, and aperture is 2nm ~ 50nm; Described outermost layer Pt-ZrO 2ratio shared by middle Pt is 20 ~ 50%, Zr simple substance and Zr alloy proportion is 10-20%, ZrO 2proportion is 30-40%, outermost layer Pt-ZrO 2in comprise Pt 3zr, PtZr, Pt 3zr 5compound.
Advantage of the present invention: have Pt-ZrO in (1) load 2layer and WC coating two-layer, the synergy between bimetallic can be given full play to.(2) surface Pt 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 is comparatively rare, thus expensive, and discontinuous structure is selected on surface, and adds ZrO 2, under the prerequisite that catalytic effect is identical, saved the cost of manufacture of catalyst.
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-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst, is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and outermost layer is Pt-ZrO 2layer; Carrier is Al 2o 3; Wherein WC layer thickness is 0.5 μm, Pt-ZrO 2layer thickness is 0.01 μm; Outermost Pt metal is discontinuous, has meso-hole structure, and aperture is 10nm; Pt-ZrO 2ratio shared by middle Pt is 40%, Zr simple substance and Zr alloy proportion is 20%, ZrO 2proportion is 40%, outermost layer Pt-ZrO 2in comprise Pt 3zr, PtZr compound.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-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst, is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and outermost layer is Pt-ZrO 2layer; Carrier is SiO 2; Wherein WC layer thickness is 10 μm, Pt-ZrO 2layer thickness is 0.1 μm; Outermost Pt metal is discontinuous, has meso-hole structure, and aperture is 50nm; Pt-ZrO 2ratio shared by middle Pt is 50%, Zr simple substance and Zr alloy proportion is 15%, ZrO 2proportion is 35%, outermost layer Pt-ZrO 2in comprise PtZr, Pt 3zr 5compound.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 (6)

1. the Pt-ZrO in a methane and carbon dioxide catalytic reforming reaction 2/ WC catalyst, is characterized in that catalyst is layer structure, and internal layer is carrier, and intermediate layer is WC layer, and outermost layer is Pt-ZrO 2layer.
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, carbon/carbon compound material.
3. catalyst according to claim 1, is characterized in that described WC layer thickness is 0.5 ~ 10 μm, Pt-ZrO 2layer thickness is 0.01 ~ 1 μm.
4. catalyst according to claim 1, it is characterized in that described outermost Pt metal is discontinuous, have meso-hole structure, aperture is 2nm ~ 50nm.
5. catalyst according to claim 1, is characterized in that described outermost layer Pt-ZrO 2ratio shared by middle Pt is 20 ~ 50%, Zr simple substance and Zr alloy proportion is 10-20%, ZrO 2proportion is 30-40%.
6. catalyst according to claim 1, is characterized in that described outermost layer Pt-ZrO 2in comprise Pt 3zr, PtZr, Pt 3zr 5compound.
CN201410604642.2A 2014-11-03 2014-11-03 Pt-ZrO2/WC (Wolfram Carbide) catalyst in methane-carbon dioxide catalytic reforming reaction Active CN104307547B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郭海军: "高分散Pt基催化剂的制备及催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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