CN115228475A - Mixed valence state nickel-based methane steam reforming catalyst and preparation method thereof - Google Patents
Mixed valence state nickel-based methane steam reforming catalyst and preparation method thereof Download PDFInfo
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- CN115228475A CN115228475A CN202210938195.9A CN202210938195A CN115228475A CN 115228475 A CN115228475 A CN 115228475A CN 202210938195 A CN202210938195 A CN 202210938195A CN 115228475 A CN115228475 A CN 115228475A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000000629 steam reforming Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000003917 TEM image Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000013112 stability test Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a mixed valence nickel-based methane steam reforming catalyst, which comprises a porous carrier and nickel species loaded on the porous carrier, wherein the proportion of nickel species mass calculated by element state to the porous carrier is 1-20%, and the nickel species comprises simple substance nickel Ni 0 And nickel oxide NiO in a molar ratio of Ni 0 /(Ni 0 + NiO) from 20% to 80%. The invention also discloses a preparation method of the catalyst.
Description
Technical Field
The invention belongs to the field of catalysts and preparation methods thereof, and particularly relates to a mixed valence nickel-based methane steam reforming catalyst and a preparation method thereof.
Background
The hydrogen is the most promising green energy in the 21 st century because of its advantages of being renewable, zero-pollution, high combustion heat value, etc. The steam methane reforming reaction is the most mature process in industry for producing hydrogen and is also the primary source of syngas, which can then be used to produce more valuable chemicals. Because of the stable carbon-hydrogen bond in the methane molecule, the progress of the methane steam reforming reaction needs to overcome very high energy barrier, and simultaneously needs the participation of a large amount of water vapor to remove the carbon deposit generated in the reaction process, so the reaction conditions of the methane steam reforming reaction in industry are harsh, generally under the pressure of 14-20atm, the reaction temperature is 800-1000 ℃, and the water-carbon ratio is 2.5-5.
Catalysts used for steam reforming of methane include mainly noble metal catalysts (Rh, pd, ir, etc.) and non-noble metal catalysts (Ni, co, fe, etc.). Noble metal catalysts show higher activity and stability in methane steam reforming reaction, but are expensive and too high in cost when used in large-scale industrial hydrogen production reaction, so that the reforming catalyst commonly used in industry at present is a non-noble metal catalyst. Among non-noble metal catalysts, ni is abundant in resources, low in price and excellent in C-H bond breaking capability, and can be catalyzed at a temperature of 600-800 ℃, so that commercial catalysts used for methane steam reforming reactions in industry are generally Ni-based catalysts. However, the Ni-based catalyst has its own disadvantages in that the stability of the catalyst is poor because metallic nickel is easily aggregated under reforming reaction conditions due to the low tamman temperature of nickel, thereby causing the deactivation of the catalyst.
With respect to the nickel-based catalyst, many researches have been conducted by researchers, which improve the performance of the nickel-based catalyst by changing the preparation method of the catalyst, replacing the catalyst carrier and adding a cocatalyst, but all of them are complicated.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention provides a mixed valence nickel-based methane steam reforming catalyst, which comprises a porous carrier and a nickel species loaded on the porous carrier, wherein the ratio of nickel to the porous carrier is 1-20% by mass of the nickel species in an elemental state, and the mixed valence nickel-based methane steam reforming catalyst is characterized in that the nickel species comprises elemental nickel Ni 0 And nickel oxide NiO in a molar ratio of Ni 0 /(Ni 0 + NiO) from 20% to 80%.
Preferably, the molar ratio of Ni 0 /(Ni 0 + NiO) is 24.4% -52.5%.
Preferably, the nickel species is supported on the porous support in the form of particles having a particle size of from 6 to 8nm, preferably from 6.5 to 7.0nm.
Preferably, the porous support is γ -Al 2 O 3 Rare earth metal oxides or molecular sieves, although other porous supports commonly used in industry may also be used, the choice of support is not critical.
A second aspect of the present invention relates to a method for preparing the mixed-valence nickel-based methane steam reforming catalyst according to the first aspect, which comprises the steps of:
(a) Impregnating the porous carrier by using a nickel salt solution, drying and calcining to prepare a catalyst precursor loaded with NiO particles on the porous carrier;
(b) And partially reducing the catalyst precursor in a reducing atmosphere to obtain the mixed-valence nickel-based methane steam reforming catalyst.
Preferably, the step (b) is performed at 550 ℃ to 800 ℃, and the reducing atmosphere is an atmosphere containing hydrogen.
More preferably, step (b) is carried out at 675 ℃ and the reducing atmosphere is a hydrogen-containing atmosphere.
Preferably, the molar ratio Ni is increased by increasing the reduction temperature 0 /(Ni 0 + NiO). In general, under the same reducing atmosphere, the higher the reducing temperature is, the Ni 0 The more the ratio, the longer the reduction time, the more NiO is. The present invention preferably sets the reduction temperature within a specific range to thereby obtain Ni in a molar ratio 0 /(Ni 0 + NiO) is controlled within a specific range, and the ratio is not as high as or low as possible, but is within a specific preferable range.
The technical scheme can be freely combined on the premise of no contradiction.
The invention has the following beneficial effects:
(1) The invention breaks through the traditional cognition that the nickel active species in the traditional nickel-based methane steam reforming catalyst must be the elemental nickel, and finds that the catalytic activity of the nickel species adopting the mixed valence state is higher.
(2) The invention is in gamma-Al 2 O 3 After the preparation of the supported nickel-based catalyst is finished, partial reduction is carried out by setting different reduction temperatures for the catalyst, and the proportion of nickel with different valence states in a catalyst system is effectively regulated and controlled, so that the aim of improving the catalyst effect is fulfilled.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of mixed-valence nickel-based methane steam reforming catalysts prepared in examples according to the present invention after reduction at different temperatures.
Fig. 2 is an X-ray photoelectron spectroscopy (XPS) graph of the mixed-valence nickel-based methane steam reforming catalyst prepared in the example of the present invention.
FIG. 3 is a graph of methane conversion and selectivity for a mixed-valence nickel-based methane steam reforming catalyst prepared in an example of the present invention.
Fig. 4 is a Transmission Electron Microscope (TEM) image of the mixed-valence nickel-based methane steam reforming catalyst prepared in the example of the present invention after reaction.
FIG. 5 is a graph showing the results of stability tests of sample b prepared in the examples of the present invention.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention.
Example 1
Firstly, 2g of gamma-Al is weighed 2 O 3 Placing into a blast oven, setting the temperature to 120 deg.C, and maintaining for 24 hr to remove gamma-Al 2 O 3 The water molecules adsorbed on the surface of the carrier enable the subsequent impregnation process to achieve better effect. 1.103g of nickel nitrate hexahydrate is weighed and dissolved in 2ml of water, and ultrasonic dissolution is carried out for 3 minutes until a clear solution is obtained. Then dripping nickel nitrate hexahydrate solution into dried gamma-Al 2 O 3 While dropwise adding, the mixture was stirred for 30 minutes, and then allowed to stand at room temperature for immersion and adsorption for 24 hours. The catalyst after impregnationThe agent was dried in an oven at 80 ℃ for 12h to remove residual moisture. And then putting the dried catalyst into a muffle furnace, raising the temperature to 600 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 4h, and cooling and taking out the catalyst to obtain the catalyst precursor loaded with NiO particles on the porous carrier.
Then putting the catalyst precursor into a fixed bed reactor, raising the temperature from room temperature to 550 ℃ under the nitrogen atmosphere, and then keeping the temperature for 1h in the hydrogen atmosphere for reducing the catalyst to obtain Ni in the catalyst 0 /(NiO+Ni 0 ) The ratio of (A) to (B) was 24.4%, the particle diameter of the nickel particles was 6.5nm, and the catalyst was named Ni/Al 2 O 3 -550℃。
Example 2
The conditions were similar to those in example 1, except that the reduction temperature of the catalyst precursor was set to 675 ℃ and then the reduction was carried out by maintaining the temperature in a hydrogen atmosphere for 1 hour to obtain a catalyst in which Ni was contained 0 /(NiO+Ni 0 ) The ratio of (A) to (B) was 40.9%, the particle diameter of the nickel particles was 6.7nm, and the catalyst was named Ni/Al 2 O 3 -675℃。
Example 3
The specific conditions were similar to those in example 1 except that the reduction temperature of the catalyst precursor was set to 725 ℃ and then maintained in a hydrogen atmosphere for 1 hour for reduction to obtain Ni in the catalyst 0 /(NiO+Ni 0 ) The ratio of (A) to (B) was 48.0%, the particle diameter of the nickel particles was 6.8nm, and the catalyst was named Ni/Al 2 O 3 -725℃。
Example 4
The conditions were similar to those in example 1, except that the reduction temperature of the catalyst precursor was set to 800 ℃ and then maintained in a hydrogen atmosphere for 1 hour for reduction to obtain Ni in the catalyst 0 /(NiO+Ni 0 ) The ratio of (A) to (B) was 52.5%, the particle size of the nickel particles was 7.0nm, and the catalyst was named Ni/Al 2 O 3 -800℃。
FIGS. 1 and 2 are TEM and XPS images of the catalyst obtained in the examples, in which a corresponds to Ni/Al 2 O 3 550 ℃ below zero, b corresponds to Ni/Al 2 O 3 675 ℃ C. C corresponds to Ni/Al 2 O 3 -725 ℃ and d pairsShould be Ni/Al 2 O 3 At-800 ℃ and the Ni/Al values are summarized in Table 1 below 2 O 3 -550℃、Ni/Al 2 O 3 -675℃、Ni/Al 2 O 3 -725℃、Ni/Al 2 O 3 The proportion of different nickel valence states at-800 ℃.
TABLE 1 proportion of nickel in different valence states in the reduced catalyst
Example 5
The catalysts obtained in the above examples 1, 2, 3 and 4 were applied to the methane steam reforming reaction at a reaction pressure of 0.1MPa and a space velocity of 20000 mL-h -1 ·g cat -1 The reaction temperature is 600 ℃, the reaction time is 4h, and the water-carbon ratio is 2.
Example 6
The Ni/Al obtained in example 2 2 O 3 The stability test of the high-temperature methane steam reforming reaction is carried out at-675 ℃, the reaction temperature is 700 ℃, the water-carbon ratio is 2, the reaction pressure is 0.1Mpa, and the space velocity is 20000 mL.h -1 ·g cat -1 。
Figure 3 shows the conversion of methane and the selectivity of the product corresponding to example 5. From FIG. 3, it can be seen that with proper Ni 0 /(NiO+Ni 0 ) Ratio of Ni/Al 2 O 3 The highest methane conversion was shown at-675 ℃. TEM characterization of the catalyst after the reaction is shown in FIG. 4, and the following Table 2 also summarizes Ni/Al before and after 4h of reaction 2 O 3 -550℃、Ni/Al 2 O 3 -675℃、Ni/Al 2 O 3 -725℃、Ni/Al 2 O 3 Particle size of nickel particles on the surface of the catalyst at-800 ℃:
TABLE 2 Change of Nickel particles before and after reaction (before/after reaction)
Ni/Al compared to catalyst before reaction 2 O 3 -725℃、Ni/Al 2 O 3 The particle diameters of nickel particles on the surface of 800 ℃ below zero are increased to 28.1nm and 35.1nm respectively, which shows that the two catalysts have poor stability and serious agglomeration of the nickel particles. And Ni/Al 2 O 3 550 ℃ below zero and Ni/Al 2 O 3 The nickel particles on the surface at the temperature of minus 675 ℃ can be kept relatively stable, the particle diameters of the nickel particles after reaction are respectively 14.1nm and 15.2nm, and the agglomeration degree is greatly reduced.
FIG. 5 shows Ni/Al 2 O 3 As a result of the stability test at-675 deg.C, ni/Al was observed 2 O 3 Conversion of methane and various product gases H in a stability test at-675 ℃ for 48H 2 The selectivity of CO and CO2 can be kept stable, which shows that the catalyst has good stability.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A mixed-valence nickel-based methane steam reforming catalyst comprises a porous carrier and a nickel species loaded on the porous carrier, wherein the ratio of nickel species mass on element basis to the porous carrier is 1% -20%, and the nickel species comprises elemental nickel (Ni) 0 And nickel oxide NiO in a molar ratio of Ni 0 /(Ni 0 + NiO) is from 20% to 80%.
2. The mixed-valence nickel-based methane steam reforming catalyst according to claim 1, wherein the molar ratio Ni is 0 /(Ni 0 + NiO) is 24.4% -52.5%.
3. The mixed-valence nickel-based methane steam reforming catalyst according to claim 1, wherein said nickel species is supported on said porous support in the form of particles having a particle size of 6-8nm.
4. The mixed-valence nickel-based methane steam reforming catalyst according to claim 3, wherein the particle size is 6.5-7.0nm.
5. The mixed-valence nickel-based methane steam reforming catalyst according to claim 1, wherein the porous support is γ -Al 2 O 3 Rare earth metal oxides or molecular sieves.
6. The method of claim 1, wherein the method comprises the steps of:
(a) Impregnating the porous carrier by using a nickel salt solution, drying and calcining to prepare a catalyst precursor loaded with NiO particles on the porous carrier;
(b) And partially reducing the catalyst precursor in a reducing atmosphere to obtain the mixed-valence nickel-based methane steam reforming catalyst.
7. The method according to claim 6, wherein the step (b) is performed at 550 ℃ to 800 ℃, and the reducing atmosphere is a hydrogen-containing atmosphere.
8. The method of claim 6, wherein step (b) is performed at 675 ℃ and the reducing atmosphere is a hydrogen-containing atmosphere.
9. The production method according to claim 6, wherein the molar ratio Ni is increased by increasing a reduction temperature 0 /(Ni 0 +NiO)。
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- 2022-08-05 CN CN202210938195.9A patent/CN115228475A/en active Pending
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