CN115739143A - Pt/alpha-MoC-CeO 2 Catalyst, preparation method thereof and application thereof in hydrogen production from methanol steam - Google Patents
Pt/alpha-MoC-CeO 2 Catalyst, preparation method thereof and application thereof in hydrogen production from methanol steam Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000011068 loading method Methods 0.000 claims abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 229910039444 MoC Inorganic materials 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
Abstract
The invention belongs to the technical field of catalysts and preparation thereof, and particularly relates to Pt/alpha-MoC-CeO 2 A catalyst for preparing hydrogen from low-temperature methanol steam, a preparation method thereof and application thereof in preparing hydrogen from methanol steam are disclosed. The catalyst comprises a carrier and an active component, wherein the carrier is alpha-MoC-CeO 2 The active component is Pt, and the loading amount of the active component in the catalyst is 0.1-20wt.%. The preparation method is simple and low in cost, the prepared catalyst is controllable in size, industrial large-scale production can be realized, and CeO 2 Can slow the oxidative deactivation of the alpha phase MoC, thereby enabling the catalyst to achieve a longer lifetime.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and particularly relates to a Pt/alpha-MoC-CeO 2 low-temperature methanol steam hydrogen production catalyst, a preparation method thereof and application thereof in methanol steam hydrogen production. .
Background
Currently, the main energy supply body of China still is fossil energy such as coal, petroleum, natural gas and the like, with the progress of human development, the defects of the fossil energy are more and more obvious, and people hope to replace the fossil energy with clean, efficient and renewable energy to generate environmental pollution, wherein the fossil energy has limited reserves. Currently, there is an increasing demand for rapid transformation from fossil energy economy to renewable energy economy, and on this background, proton exchange membrane fuel cells that generate electricity for various mobile devices using hydrogen gas are gaining wide attention due to their advantages of high efficiency, cleanliness, and sustainability. However, because of the physical and chemical properties of hydrogen as a combustible gas, the storage and transportation of hydrogen become a great resistance to the development of proton exchange membrane fuel cells, and one of the solutions to this problem is to utilize liquid fuel to reform hydrogen in situ. Methanol steam reforming reaction (MSR) has been extensively and intensively studied as one of the most promising on-site reforming hydrogen production reactions due to its mild reaction conditions and high hydrogen production capacity and the advantage of methanol as a liquid fuel for easy storage and transportation.
Currently MSR reaction (CH) is used 3 OH+H 2 O→CO 2 +3H 2 ) The common commercial catalysts for reforming hydrogen production are Cu/ZnO and Cu/Zn/Al represented by Cu base 2 O 3 The temperature of use is often between 250 ℃ and 350 ℃. When the temperature is lower than 250 ℃, the activity of the commercial Cu-based catalyst is greatly reduced. The use temperature of the Cu-based commercial catalyst is higher than that of the high-temperature proton exchange membrane fuel cell, so that the power density of the high-temperature proton exchange membrane fuel cell system is difficult to further increase. Therefore, the development of the MSR reaction catalyst with excellent performance under the conditions of normal pressure and low temperature has important significance for improving the performance of a high-temperature polymer electrolyte membrane fuel cell system.
Disclosure of Invention
The invention aims to provide Pt/alpha-MoC-CeO 2 A catalyst, a preparation method thereof and application thereof in hydrogen production by methanol steam. The catalyst can perform the hydrogen production reaction by methanol steam reforming under the conditions of normal pressure and low temperature, and solves the problem that the commercial catalyst for the hydrogen production reaction by methanol steam reforming has overhigh use temperature.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
Pt/alpha-MoC-CeO 2 The catalyst for low-temperature methanol steam reforming hydrogen production is characterized in that: the MoC structure is a sheet structure, and the oxidation inactivation of alpha-MoC is delayed by introducing Ce, so that the catalyst can realize high activity for a long time at a lower temperature.
One aspect of the invention provides Pt/alpha-MoC-CeO 2 The catalyst comprises a carrier and an active component, wherein the carrier is alpha-MoC-CeO 2 The active component is Pt, and the loading amount of the active component in the catalyst is 0.1-20wt.%.
In the above technical solution, further, ceO is contained in the carrier 2 The mole fraction of (A) is 0.01-30%.
In the above technical scheme, further, in the catalyst, the particle size of the active component Pt is 10-50nm, and the particle size of the carrier is 0.1-5 μm.
In another aspect, the present invention provides a method for preparing the above catalyst, comprising the following steps:
(1) Adding MoO 3 Dissolving in water to obtain a solution A, and dissolving cerium nitrate in water to obtain a solution B;
(2) Under the condition of stirring, uniformly mixing the solution A and the solution B obtained in the step (1), then dropwise adding a chloroplatinic acid solution, and uniformly stirring and dispersing;
(3) Evaporating the liquid in the mixture obtained in the step (2) to dryness, drying the obtained solid, and then putting the solid into a muffle furnace for calcining to obtain Pt/MoO 3 -CeO 2 A precursor;
(4) The Pt/MoO obtained in the step (3) is treated 3 -CeO 2 The precursor is put into a vertical muffle furnace in CH 4 /H 2 Carrying out temperature programmed carburization in a mixed atmosphere, and then cooling to room temperature in the original atmosphere;
(5) Passing gas from CH 4 /H 2 Switching to oxygen and argon mixed gas with the volume fraction of 1-10% of oxygen for passivation to obtain Pt/alpha-MoC-CeO 2 A catalyst.
In the above technical solution, further, in the step (1), moO 3 The preparation method comprises the following steps:
grinding ammonium heptamolybdate into powder, putting the powder into a muffle furnace, heating to 300-600 ℃, and keeping for 1-12h to obtain MoO 3 。
In the above technical solution, further, in the step (2), moO in the solution a 3 The concentration of (A) is 0.05-1mol/L, and the concentration of the cerium nitrate in the solution B is 0.01-0.5mol/L.
In the above technical solution, further, in the step (3), the evaporation is performed by using a rotary vacuum evaporation apparatus; the drying temperature is 60-150 ℃, and the drying time is 1-12h; the calcination temperature is 300-600 ℃, the calcination is kept for 1-12h, and the temperature programming rate is 1-10 ℃.
In the above technical scheme, further, in the step (4), the carburization end point temperature is 600-800 ℃, and is kept at the temperature for 1-6h, and the programmed heating rate is 1-10 ℃/min.
In the above technical solution, further, in the step (5), the passivation time is 1-12h.
The invention also provides an application of the catalyst in hydrogen production by methanol steam, wherein the hydrogen production reaction is carried out on methanol and water under the action of the catalyst to obtain hydrogen; the reaction conditions include: under normal pressure, the temperature is 120-300 ℃, the molar ratio of water to methanol is 1-5, and the mass space velocity of methanol is WHSV =0.5-5h -1 。
The catalyst is in a porous structure, the MoC structure is in a sheet structure, and the oxidation inactivation of alpha-MoC is delayed by introducing Ce, so that the catalyst can realize high activity for a long time at a lower temperature.
The invention has the following beneficial effects:
(1) The preparation method is simple and low in cost, and the prepared catalyst is controllable in size and can realize industrial large-scale production.
(2)CeO 2 Can slow the oxidative deactivation of the alpha phase MoC, thereby allowing the catalyst to achieve longer life.
(3)Pt/α-MoC-CeO 2 At low temperature and normal pressureUnder the condition, the catalytic activity is obviously higher than that of the commercial CuZnAlO x A methanol steam reforming catalyst.
Drawings
FIG. 1 shows Pt/α -MoC-CeO prepared in examples 1 to 3 2 And X-ray diffraction pattern (XRD) of the Pt/α -MoC catalyst prepared in comparative example 1;
FIG. 2 shows Pt/α -MoC-CeO obtained in example 1 2 Scanning Electron Microscopy (SEM) of the catalyst;
FIG. 3 shows Pt/α -MoC-CeO obtained in example 1 2 Catalyst and commercial CuZnAlO of comparative example 2 x A catalyst is used for catalyzing the conversion rate of methanol under the same condition;
FIG. 4 shows Pt/α -MoC-CeO obtained in example 1 2 Comparative example 1 and comparative example 1.
Detailed Description
Example 1
(1) 5g of ammonium heptamolybdate (NH) are taken 4 ) 6 Mo 7 O 24 Grinding into powder, placing into a muffle furnace, heating to 500 deg.C at a rate of 5K/min, and maintaining for 4 hr to obtain MoO 3 ；
(2) Taking 1.2105g of MoO prepared in the step (1) 3 Dissolving in 50ml of deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 2h, dissolving 0.1827g of cerium nitrate in 50ml of deionized water, and placing in the ultrasonic cleaning machine for ultrasonic treatment for 2h;
(3) Under the stirring state, moO 3 Dropwise adding the solution into a cerous nitrate solution, carrying out ultrasonic treatment for 2h, then dropwise adding a chloroplatinic acid solution containing 20mg of Pt under a stirring state, carrying out ultrasonic treatment for 2h, and immediately stirring for 12h after the ultrasonic treatment is finished;
(4) Evaporating the liquid in the mixture obtained in the step (3) to dryness by using a rotary vacuum evaporator, drying the mixture in a vacuum drying oven at 110 ℃ for 6 hours, putting the obtained solid in a muffle furnace, heating the solid to 500 ℃ at the speed of 10 ℃/min, and keeping the temperature for 4 hours to obtain Pt/MoO 3 -CeO 2 A precursor;
(5) The Pt/MoO obtained in the step (4) is treated 3 -CeO 2 The precursor is placed in a vertical muffle furnace at CH 4 /H 2 (20%/80% v/v) performing temperature programmed carburization under a mixed atmosphere, the temperature programmed to directly raise the temperature at a rate of 5 ℃/min to 700 ℃ and maintain it at that temperature for 2 hours, followed by lowering to room temperature under the original atmosphere;
(6) Cooling to room temperature, and introducing gas from CH 4 /H 2 Switching to O with an oxygen volume fraction of 1% 2 And passivating the Ar mixed gas for 2 hours.
Example 2
(1) 5g of ammonium heptamolybdate (NH) are taken 4 ) 6 Mo 7 O 24 Grinding into powder, placing into a muffle furnace, heating to 500 deg.C at a rate of 5K/min, and maintaining for 4 hr to obtain MoO 3 ；
(2) Taking 1.1370g of MoO prepared in the step (1) 3 Dissolving in 50ml of deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 2h, dissolving 0.3402g of cerium nitrate in 50ml of deionized water, and placing in the ultrasonic cleaning machine for ultrasonic treatment for 2h;
(3) Under the stirring state, moO 3 Dropwise adding the solution into a cerium nitrate solution, carrying out ultrasonic treatment for 2h, then dropwise adding a chloroplatinic acid solution containing 20mgPt under a stirring state, carrying out ultrasonic treatment for 2h, and immediately stirring for 12h after the ultrasonic treatment is finished;
(4) Evaporating the liquid in the mixture obtained in the step (3) to dryness by using a rotary vacuum evaporator, drying the mixture in a vacuum drying oven at 110 ℃ for 6 hours, putting the obtained solid in a muffle furnace, heating the solid to 500 ℃ at the speed of 10 ℃/min, and keeping the temperature for 4 hours to obtain Pt/MoO 3 -CeO 2 A precursor;
(5) The Pt/MoO obtained in the step (4) is treated 3 -CeO 2 The precursor is placed in a vertical muffle furnace at CH 4 /H 2 (20%/80% v/v) performing temperature programmed carburization under a mixed atmosphere, the temperature programmed to directly raise the temperature at a rate of 5 ℃/min to 700 ℃ and maintain it at that temperature for 2 hours, followed by lowering to room temperature under the original atmosphere;
(6) Cooling to room temperature, and introducing gas from CH 4 /H 2 Switching to O with an oxygen volume fraction of 1% 2 And passivating the Ar mixed gas for 2 hours.
Example 3
(1) 5g of heptamolybdic acid are takenAmmonium (NH) 4 ) 6 Mo 7 O 24 Grinding into powder, placing into a muffle furnace, heating to 500 deg.C at a rate of 5K/min, and maintaining for 4 hr to obtain MoO 3 ；
(2) 0.9909g of MoO prepared in step (1) was taken 3 Dissolving in 50ml of deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 2 hours, dissolving 0.598g of cerium nitrate in 50ml of deionized water, and placing in the ultrasonic cleaning machine for ultrasonic treatment for 2 hours;
(3) Under the stirring state, moO 3 Dropwise adding the solution into a cerium nitrate solution, carrying out ultrasonic treatment for 2h, then dropwise adding a chloroplatinic acid solution containing 20mgPt under a stirring state, carrying out ultrasonic treatment for 2h, and immediately stirring for 12h after the ultrasonic treatment is finished;
(4) Then evaporating the liquid in the mixture obtained in the step (3) to dryness by using a rotary vacuum evaporator, drying the mixture in a vacuum drying oven at 110 ℃ for 6 hours, putting the obtained solid in a muffle furnace, heating the solid to 500 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4 hours to obtain Pt/MoO 3 -CeO 2 A precursor;
(5) The Pt/MoO obtained in the step (4) is used 3 -CeO 2 The precursor is placed in a vertical muffle furnace at CH 4 /H 2 (20%/80% v/v) performing temperature programmed carburization under a mixed atmosphere, the temperature programmed to directly raise the temperature at a rate of 5 ℃/min to 700 ℃ and maintain it at that temperature for 2 hours, followed by lowering to room temperature under the original atmosphere;
(6) After cooling to room temperature, the gas is removed from CH 4 /H 2 Switching to O with an oxygen volume fraction of 1% 2 And passivating the Ar mixed gas for 2 hours.
Comparative example 1
Comparative example 1 no Ce was added and the specific preparation method was as follows:
(1) 5g of ammonium heptamolybdate (NH) were taken 4 ) 6 Mo 7 O 24 Grinding into powder, placing into a muffle furnace, heating to 500 deg.C at a rate of 5K/min, and maintaining for 4 hr to obtain MoO 3 ；
(2) Taking 1.3084g of MoO prepared in the step (1) 3 Dissolving in 50ml deionized water, and placing in an ultrasonic cleaning machine for ultrasonic treatment for 2h;
(3) Dropwise adding chloroplatinic acid solution containing 20mg of Pt under the stirring state, carrying out ultrasonic treatment for 2h, and immediately stirring for 12h after finishing ultrasonic treatment;
(4) Evaporating the liquid in the mixture obtained in the step (3) to dryness by using a rotary vacuum evaporator, drying the mixture in a vacuum drying oven at 110 ℃ for 6 hours, putting the obtained solid in a muffle furnace, heating the solid to 500 ℃ at the speed of 10 ℃/min, and keeping the temperature for 4 hours to obtain Pt/MoO 3 -CeO 2 A precursor;
(5) The Pt/MoO obtained in the step (4) is used 3 -CeO 2 The precursor is put into a vertical muffle furnace in CH 4 /H 2 (20%/80% v/v) performing temperature programmed carburization under a mixed atmosphere, the temperature programmed to directly raise the temperature at a rate of 5 ℃/min to 700 ℃ and maintain it at that temperature for 2 hours, followed by lowering to room temperature under the original atmosphere;
(6) Cooling to room temperature, and introducing gas from CH 4 /H 2 Switching to O with an oxygen volume fraction of 1% 2 And passivating the Ar mixed gas for 2 hours.
Comparative example 2
Comparative example 2 is commercial CuZnAlO x A catalyst.
FIG. 1 shows Pt/α -MoC-CeO prepared in examples 1 to 3 2 X-ray diffraction patterns (XRD) of the catalyst and comparative example 1Pt/α -MoC without introduced Ce, it can be seen that the addition of Ce does not change the phase state of MoC, which remains as the α phase. In addition, with the increase of the doping amount of Ce, the characteristic peak of Pt is gradually weakened, which shows that the addition of Ce can well promote the dispersion of Pt, thereby avoiding the phenomenon of Pt particle aggregation. And with the increase of the doping amount of Ce, the characteristic peak strength of MoC is gradually reduced, and the half-peak width is gradually increased. This indicates that as the doping amount of Ce increases, the particle size of MoC gradually decreases, and a larger specific surface area is formed, so that the active sites have more exposure opportunities, thereby improving the catalytic activity.
FIG. 2 is a diagram of Pt/α -MoC-CeO prepared in example 1 2 Scanning Electron Microscope (SEM) images of the catalyst show that the morphology of the molybdenum carbide carrier is a smooth sheet structure, and no obvious cracks are observed. No significant Pt particles were observed on the molybdenum carbide surface in the figure, indicating that the incorporation of Ce makes Pt more uniformly dispersed on the molybdenum carbide surfaceAnd (6) homogenizing.
Example 4
In a fixed bed reactor, the reaction conditions are: normal pressure, reaction temperature of 200 ℃, residence time of 0-500kg s.mol -1 Test Pt/α -MoC-CeO prepared in example 1 at a hydroalcoholic ratio of 1.5 for 1 hour 2 Catalyst and commercial CuZnAlO of comparative example 2 x The catalyst catalyzes the conversion of methanol.
FIG. 3 shows Pt/α -MoC-CeO prepared in example 1 2 Catalyst and commercial CuZnAlO of comparative example 2 x The catalyst catalyzes a methanol conversion rate contrast chart under the same conditions. It can be seen from the graph that Pt/alpha-MoC-CeO prepared in example 1 is at 200 deg.C 2 The residence time of the catalyst in the reactor is 100kg s mol -1 The methanol conversion is close to 100%, while the commercial CuZnAlO of comparative example 2 is obtained under the same test conditions x The conversion rate of the catalyst is only 26%, and the catalytic activity of the catalyst is obviously higher than that of the commercial CuZnAlO under the low-temperature condition x The catalyst is a low-temperature methanol steam reforming hydrogen production catalyst with wide application prospect.
Example 5 in a fixed bed reactor, the reaction conditions were: normal pressure, reaction temperature of 350 ℃, retention time of 200kg s mol -1 The Pt/alpha-MoC-CeO prepared in example 1 was tested at a hydroalcoholic ratio of 1.5 for 1-5 hours 2 Catalyst and Pt/MoO prepared in comparative example 1 3 -CeO 2 The catalytic activity life of the catalyst.
FIG. 4 shows Pt/α -MoC-CeO obtained in example 1 2 Comparative figure of the catalyst and comparative example 1 in the same test conditions of the catalytic activity life test. It can be seen from the graph that the catalytic activities of comparative example 1 and example 1 both decreased with the progress of the reaction time, but the decrease rate of example 1 was lower than that of comparative example 1. This indicates that the present invention delays the deactivation of the catalyst and extends its life.
Claims (10)
1. Pt/alpha-MoC-CeO 2 The catalyst is characterized by comprising a carrier and an active component, wherein the carrier is alpha-MoC-CeO 2 The active component is Pt, and in the catalyst, the active componentThe loading of the component is 0.01-20wt.%.
2. The catalyst of claim 1 wherein the carrier is CeO 2 The mole fraction of (A) is 0.01-30%.
3. The catalyst according to claim 1, wherein the particle size of the active component Pt in the catalyst is 10-50nm, and the particle size of the carrier is 0.01-5 μm.
4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) Adding MoO 3 Dissolving in water to obtain a solution A, and dissolving cerium nitrate in water to obtain a solution B;
(2) Under the condition of stirring, uniformly mixing the solution A and the solution B obtained in the step (1), then dropwise adding a chloroplatinic acid solution, and uniformly stirring and dispersing;
(3) Evaporating the liquid in the mixture obtained in the step (2) to dryness, drying the obtained solid, and then putting the solid into a muffle furnace for calcining to obtain Pt/MoO 3 -CeO 2 A precursor;
(4) The Pt/MoO obtained in the step (3) is treated 3 -CeO 2 The precursor is placed in a vertical muffle furnace at CH 4 /H 2 Carrying out temperature programmed carburization in a mixed atmosphere, and then cooling to room temperature in the original atmosphere;
(5) Passing gas from CH 4 /H 2 Switching to oxygen and argon mixed gas with the volume fraction of 1-10% of oxygen for passivation to obtain Pt/alpha-MoC-CeO 2 A catalyst.
5. The method according to claim 4, wherein in the step (1), moO 3 The preparation method comprises the following steps:
grinding ammonium heptamolybdate into powder, putting the powder into a muffle furnace, heating to 300-600 ℃, and keeping for 1-12h to obtain MoO 3 。
6. The method according to claim 4, wherein in the step (2), moO is contained in the solution A 3 The concentration of (A) is 0.05-1mol/L, and the concentration of the cerium nitrate in the solution B is 0.01-0.5mol/L.
7. The preparation method according to claim 4, wherein in the step (3), the evaporation is performed by a rotary vacuum evaporation apparatus; the drying temperature is 60-150 ℃, and the drying time is 1-12h; the calcination temperature is 300-600 ℃, the calcination is kept for 1-12h, and the temperature programming rate is 1-10 ℃.
8. The method according to claim 4, wherein in the step (4), the carburization end point temperature is 600 ℃ to 800 ℃ and is maintained at the temperature for 1 to 6 hours, and the temperature programming rate is 1 to 10 ℃/min.
9. The method according to claim 4, wherein in the step (5), the passivation time is 1-12h.
10. A Pt/α -MoC-CeO according to any one of claims 1 to 3 2 The application of the catalyst or the catalyst prepared by the preparation method of any one of claims 4 to 9 in the hydrogen production from methanol steam is characterized in that the methanol and water are subjected to hydrogen production reaction under the action of the catalyst to obtain hydrogen; the reaction conditions include: under normal pressure, the temperature is 120-300 ℃, the mol ratio of water to methanol is 1-5, and the mass space velocity of methanol is WHSV =0.5-5h -1 。
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