CN104289241B - A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2the preparation method of/WC catalyst - Google Patents
A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2the preparation method of/WC catalyst Download PDFInfo
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- CN104289241B CN104289241B CN201410604641.8A CN201410604641A CN104289241B CN 104289241 B CN104289241 B CN 104289241B CN 201410604641 A CN201410604641 A CN 201410604641A CN 104289241 B CN104289241 B CN 104289241B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 11
- 239000001569 carbon dioxide Substances 0.000 title claims description 11
- 238000001833 catalytic reforming Methods 0.000 title claims description 9
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 title claims description 7
- 239000000969 carrier Substances 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- 238000009413 insulation Methods 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005255 carburizing Methods 0.000 claims abstract description 6
- 238000005296 abrasive Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001722 carbon compounds Chemical class 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052904 quartz Inorganic materials 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 4
- 206010011376 Crepitations Diseases 0.000 abstract description 2
- 210000002381 Plasma Anatomy 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 230000002194 synthesizing Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N Magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N Tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Abstract
The present invention provides the preparation method of the transition-metal catalyst that a kind of Pt race metal intersperses active site, first process and ultrasonic cleaning carrier surface with abrasive paper for metallograph, after drying, carrier is placed on double brightness stove negative electrode, carbon target is placed on source electrode, die opening is set, cathode voltage, source voltage etc., evacuation leads to argon, carburizing under plasma bombardment, it is down to room temperature after insulation a period of time, on carrier, i.e. obtain carbon-coating, the most in kind change parameter and ooze tungsten, the coating high-temperature process in 1000 ~ 2000 DEG C of normal pressure argon gas atmosphere that will make, continue Pt Zr to ooze altogether, high-temperature process promotes Pt race metal recrystallization to be formed mesoporous, final high temperature oxidation promotes Zr to be converted into ZrO2.This method deposition velocity is fast, and the carrier side back side has all been coated with coating, and coating uniform is fine and close, does not haves crackle, combines preferably between carrier and coating, and the catalyst prepared has preferably catalysis activity and coking resistivity.
Description
Technical field
The present invention relates to the preparation method of a kind of catalyst, particularly relate to the Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction2The preparation method of/WC catalyst.
Background technology
Methane is the main component of natural gas, and along with the exhaustion day by day of petroleum resources, the natural gas resource of rich reserves will become one of the most desired alternative energy source.In the face of huge resources advantage, natural gas utilize level the lowest.Therefore, natural gas is converted into by means such as chemical catalysis liquid fuel or the chemical products of high added value being prone to transport, is paid close attention to by researcheres numerous in world wide.In general, methane synthesis gas has three approach: i.e. steam reforming, methane portion oxidation and CO 2 reformation.H during wherein CO 2 reformation synthetic gas production process has the advantage that the synthesis gas that (1) produces2/ CO ratio about 1, can compensate for, directly as the raw material of oxo process, the deficiency that in the synthesis gas that steam reforming prepares, C/Hratio is higher；(2) make use of the methane and carbon dioxide both gas to earth harm maximum simultaneously, improve the ecological environment of the mankind；(3) methane-CO 2 reformation is the reversible reaction with bigger reaction heat, can be as the medium of energy storage.This process is a strong endothermic reaction (H=248 kJ/mo l), needs higher reaction temperature (800 DEG C).Therefore, the catalyst developing high activity, high selection and high stable is one of methyl hydride catalyzed reformation key factor realizing commercial Application, is also the focus in this area research.
VIIIth group 4 transition metal catalyst (in addition to Os), the carbide etc. of W all have preferable reactivity and coking resistivity, thus can be as the catalyst of methane and carbon dioxide catalytic reforming reaction.If with bimetallic as active component, owing to producing certain synergism between bimetallic, an effect mutually promoted can be obtained, therefore bimetallic catalyst has more superior catalysis activity and coking resistivity.In numerous type catalyst, meso-hole structure catalyst has bigger specific surface area and pore volume, the features such as preferable anti-carbon deposit and anti-agglutinatting property, development in recent years is rapid, but catalyst structure more options carrier structure is meso-hole structure at present, consumption is relatively large, but selects load the most rarely found for the catalyst of meso-hole structure.Catalyst performance and carrier, the preparation method etc. of catalyst also have close relationship, and the difference of preparation method, the performance of catalyst can present larger difference.
The Chinese patent of Application No. 201110102844.3 discloses a kind of method of synthesizing gas by reforming methane with co 2, belong to organic chemical industry and field of catalyst preparation, it is characterized in that a kind of using one or multi-step infusion process each for catalyst active component and auxiliary agent to be supported on carrier, and the technical scheme of catalytic methane CO 2 reformation preparing synthetic gas at ambient pressure.Use the predecessor after one or many dipping, through standing, being dried, roasting, after reduction, can be directly used for fixed bed synthesizing gas by reforming methane with co 2.Catalyst prepared by the method is at 1atm, under the conditions of 800 DEG C and GHSV=1.2 × 104h-1,90% and above methane conversion stable at 860h, 90% and above carbon dioxide conversion stably at 960h.When reaction proceeds to 1000h, catalyst is to CH4Conversion ratio 70%, to CO2Conversion ratio 86%.
The Chinese patent of Application No. 201110102844.3 discloses a kind of methane carbon dioxide reformation nickel-base catalyst obtaining synthesis gas and preparation method thereof, first step preparation mixed solution: with Ni (NO3)2·6H2O、Mg(NO3)2·6H2O and deionized water are preparation of raw material mixed solution；In this mixed solution, Ni (NO3)2
Concentration be 0.2 mol/L to 0.5mol/L, Mg (NO3)2Concentration is 0.3 mol/L to 0.6mol/L；Prepared by second step: first by γ-Al2O3
Add in Rotary Evaporators, heating, evacuation, it is heated to 40 DEG C to 60 DEG C, vacuum reaches under 0.065MPa to 0.085MPa, keeps 5 minutes to 10 minutes；Under above-mentioned vacuum, above-mentioned first step gained mixed solution is added in above-mentioned Rotary Evaporators, and makes the solid in Rotary Evaporators be totally submerged in mixed solution；Under above-mentioned vacuum, keep liquidus temperature 30 DEG C to 50 DEG C, in rotating condition, maintain 20 hours to 30 hours；Then, under above-mentioned vacuum and rotation, it is warmed up to 60 DEG C to 80 DEG C, is dried or is evaporated to, without liquid phase, obtain solid content；Finally, at 650 DEG C to 750 DEG C, by this solid content roasting 4 hours to 6 hours, i.e. prepare nickel-base catalyst.
Two above patent can prepare the catalyst of methane and carbon dioxide catalytic reforming reaction, but the adhesion between active component and carrier is poor, and active component easily comes off；In addition, technique is relative complex, and sedimentation rate is relatively slow, and work efficiency is relatively low.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that the Pt-ZrO in a kind of methane and carbon dioxide catalytic reforming reaction2The preparation method of/WC catalyst, it is characterised in that comprise the following steps:
(1) with abrasive paper for metallograph process and ultrasonic cleaning carrier surface, post-drying；
(2) being put into by carrier on double brightness stove negative electrode, be placed on by carbon target on double brightness stove source electrode, and the distance between carrier is 10 ~ 20mm, regulation cathode voltage is to 400 ~ 500V, source voltage to 850 ~ 900V, and evacuation is passed through argon；
(3) with the ramp of 10 ~ 50 DEG C/min to 700 ~ 900 DEG C, under 10 ~ 48Pa operating air pressure, carry out carburizing, take out after being cooled to room temperature with the speed of 1 ~ 10 DEG C/min after insulation 1 ~ 3h；
(4) being put into by the carrier oozing carbon on double brightness stove negative electrode, be placed on by tungsten target on double brightness stove source electrode, and the distance between carrier is 20 ~ 25mm, regulation cathode voltage is to 410 ~ 460V, source voltage to 810 ~ 860V, and evacuation is passed through argon；
(5) with the ramp of 10 ~ 50 DEG C/min to 700 ~ 950 DEG C, under 10 ~ 48Pa operating air pressure, carry out oozing tungsten, take out after being cooled to room temperature with the speed of 1 ~ 10 DEG C/min after insulation 1 ~ 3.5h；
(6) by the coating for preparing at 1000 ~ 2000 DEG C, high-temperature process 0.1 ~ 1h in normal pressure argon gas atmosphere；
(7) by oozing carbon, the carrier of tungsten put on double brightness stove negative electrode, Pt-Zr alloys target is placed on double brightness stove source electrode, and the distance between carrier is 20 ~ 25mm, regulation cathode voltage is to 500 ~ 600V, source voltage to 900 ~ 950V, and evacuation is passed through argon；
(8) with the ramp of 10 ~ 50 DEG C/min to 700 ~ 950 DEG C, under 10 ~ 48Pa operating air pressure, carry out oozing Pt-Zr, take out after being cooled to room temperature with the speed of 1 ~ 10 DEG C/min after insulation 1 ~ 3.5h；
(9) by the coating for preparing at 1000 ~ 2000 DEG C, high-temperature process 0.1 ~ 1h in atmospheric hydrogen atmosphere；
(10) at a temperature of 500 ~ 1000 DEG C, top layer Pt-Zr layer is aoxidized.
Described carrier is Al2O3、MgO、SiO2、TiO2、ZrO2, foamed ceramics, rare-earth oxide, composite oxides or carbon/carbon compound material.
Advantages of the present invention: the deposition velocity of (1) coating is very fast, substantially increases efficiency prepared by coating.(2) producing highdensity plasma cloud between target and carrier, the back side, side of carrier has all been coated with coating.(3) carburizing is oozed after tungsten terminates, and also carries out high-temperature process, carbon-coating and tungsten layer and is converted into tungsten carbide coating, and coating uniform is fine and close, does not haves crackle, combines preferably between carrier and coating.(4) ooze after Pt-Zr terminates, carry out high-temperature process, promote Pt recrystallization, define active site, and then surface Pt is provided with meso-hole structure, enhance catalysis activity and the coking resistivity of material.
Detailed description of the invention
Below in conjunction with specific embodiment, it is further elucidated with the present invention, it should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention, after having read the present invention, those skilled in the art all fall within the application claims to the amendment of the various equivalent form of values of the present invention and are limited.
Embodiment 1
A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2The preparation method of/WC catalyst, it is characterised in that comprise the following steps:
(1) process and ultrasonic cleaning SiO with abrasive paper for metallograph2Carrier surface, post-drying；
(2) being put into by carrier on double brightness stove negative electrode, be placed on by carbon target on double brightness stove source electrode, and the distance between carrier is 20mm, regulation cathode voltage is to 500V, source voltage to 900V, and evacuation is passed through argon；
(3) with the ramp of 50 DEG C/min to 900 DEG C, under 48Pa operating air pressure, carry out carburizing, take out after being cooled to room temperature with the speed of 10 DEG C/min after insulation 3h；
(4) being put into by the carrier oozing carbon on double brightness stove negative electrode, be placed on by tungsten target on double brightness stove source electrode, and the distance between carrier is 25mm, regulation cathode voltage is to 460V, source voltage to 860V, and evacuation is passed through argon；
(5) with the ramp of 50 DEG C/min to 950 DEG C, under 48Pa operating air pressure, carry out oozing tungsten, take out after being cooled to room temperature with the speed of 10 DEG C/min after insulation 3.5h；
(6) by the coating for preparing at 2000 DEG C, high-temperature process 1h in normal pressure argon gas atmosphere；
(7) by oozing carbon, the carrier of tungsten put on double brightness stove negative electrode, Pt-Zr alloys target is placed on double brightness stove source electrode, and the distance between carrier is 25mm, regulation cathode voltage is to 600V, source voltage to 950V, and evacuation is passed through argon；
(8) with the ramp of 50 DEG C/min to 950 DEG C, under 48Pa operating air pressure, carry out oozing Pt-Zr, take out after being cooled to room temperature with the speed of 10 DEG C/min after insulation 3.5h；
(9) by the coating for preparing at 2000 DEG C, high-temperature process 1h in atmospheric hydrogen atmosphere；
(10) at a temperature of 1000 DEG C, top layer Pt-Zr layer is aoxidized.
Embodiment 2
A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2The preparation method of/WC catalyst, it is characterised in that comprise the following steps:
(1) process and ultrasonic cleaning Al with abrasive paper for metallograph2O3Carrier surface, post-drying；
(2) being put into by carrier on double brightness stove negative electrode, be placed on by carbon target on double brightness stove source electrode, and the distance between carrier is 15mm, regulation cathode voltage is to 450V, source voltage to 850V, and evacuation is passed through argon；
(3) with the ramp of 25 DEG C/min to 800 DEG C, under 35Pa operating air pressure, carry out carburizing, take out after being cooled to room temperature with the speed of 5 DEG C/min after insulation 2h；
(4) being put into by the carrier oozing carbon on double brightness stove negative electrode, be placed on by tungsten target on double brightness stove source electrode, and the distance between carrier is 20mm, regulation cathode voltage is to 430V, source voltage to 830V, and evacuation is passed through argon；
(5) with the ramp of 25 DEG C/min to 850 DEG C, under 35Pa operating air pressure, carry out oozing tungsten, take out after being cooled to room temperature with the speed of 5 DEG C/min after insulation 2h；
(6) by the coating for preparing at 1500 DEG C, high-temperature process 0.5h in normal pressure argon gas atmosphere；
(7) by oozing carbon, the carrier of tungsten put on double brightness stove negative electrode, Pt-Zr alloys target is placed on double brightness stove source electrode, and the distance between carrier is 20mm, regulation cathode voltage is to 500V, source voltage to 900V, and evacuation is passed through argon；
(8) with the ramp of 25 DEG C/min to 850 DEG C, under 35Pa operating air pressure, carry out oozing Pt-Zr, take out after being cooled to room temperature with the speed of 5 DEG C/min after insulation 2h；
(9) by the coating for preparing at 1500 DEG C, high-temperature process 0.5h in atmospheric hydrogen atmosphere；
(10) at a temperature of 500 DEG C, top layer Pt-Zr layer is aoxidized.
Above are only two detailed description of the invention of the present invention, but the design concept of the present invention is not limited thereto, all changes utilizing this design that the present invention carries out unsubstantiality, the behavior invading the scope of protection of the invention all should be belonged to.In every case it is the content without departing from technical solution of the present invention, any type of simple modification, equivalent variations and remodeling above example made according to the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (2)
1. the Pt-ZrO in a methane and carbon dioxide catalytic reforming reaction2The preparation method of/WC catalyst, it is characterised in that include with
Lower step:
(1) with abrasive paper for metallograph process and ultrasonic cleaning carrier surface, post-drying；
(2) carrier is put on double brightness stove negative electrode, carbon target is placed on double brightness stove source electrode, and the distance between carrier is
10～20mm, regulation cathode voltage is to 400～500V, and source voltage to 850～900V, evacuation is passed through argon；
(3) with the ramp of 10～50 DEG C/min to 700～900 DEG C, under 10～48Pa operating air pressures, carburizing is carried out, insulation
Take out after being cooled to room temperature with the speed of 1～10 DEG C/min after 1～3h；
(4) carrier oozing carbon is put on double brightness stove negative electrode, tungsten target is placed on double brightness stove source electrode, and the distance between carrier is
20～25mm, regulation cathode voltage is to 410～460V, and source voltage to 810～860V, evacuation is passed through argon；
(5) with the ramp of 10～50 DEG C/min to 700～950 DEG C, under 10～48Pa operating air pressures, tungsten is carried out oozing, insulation
Take out after being cooled to room temperature with the speed of 1～10 DEG C/min after 1～3.5h；
(6) by the coating for preparing at 1000～2000 DEG C, high-temperature process 0.1～1h in normal pressure argon gas atmosphere；
(7) by oozing carbon, the carrier of tungsten put on double brightness stove negative electrode, Pt-Zr alloys target is placed on double brightness stove source electrode, with carrier it
Between distance be 20～25mm, regulation cathode voltage to 500～600V, source voltage to 900～950V, evacuation is passed through argon
Gas；
(8) with the ramp of 10～50 DEG C/min to 700～950 DEG C, under 10～48Pa operating air pressures, Pt-Zr is carried out oozing, insulation
Take out after being cooled to room temperature with the speed of 1～10 DEG C/min after 1～3.5h；
(9) by the coating for preparing at 1000～2000 DEG C, high-temperature process 0.1～1h in atmospheric hydrogen atmosphere；
(10) at a temperature of 500～1000 DEG C, top layer Pt-Zr layer is aoxidized.
Preparation method the most according to claim 1, it is characterised in that described carrier is Al2O3、MgO、SiO2、TiO2、
ZrO2, foamed ceramics, rare-earth oxide, composite oxides or carbon/carbon compound material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604641.8A CN104289241B (en) | 2014-11-03 | A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2the preparation method of/WC catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604641.8A CN104289241B (en) | 2014-11-03 | A kind of Pt-ZrO in methane and carbon dioxide catalytic reforming reaction2the preparation method of/WC catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104289241A CN104289241A (en) | 2015-01-21 |
| CN104289241B true CN104289241B (en) | 2017-01-04 |
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Citations (2)
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|---|---|---|---|---|
| CN101648140A (en) * | 2008-08-14 | 2010-02-17 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose |
| 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 (2)
| 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 |
| CN101648140A (en) * | 2008-08-14 | 2010-02-17 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose |
Non-Patent Citations (2)
| Title |
|---|
| 碳钢表面双辉等离子渗镀WC陶瓷膜的工艺探索及性能研究;姜云冬;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110615;摘要及第12-16页 * |
| 高分散Pt基催化剂及催化性能研究;郭海军;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110315;第43页 * |
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