CN106000405B - A kind of multi-stage porous loading type nickel-based catalyst, preparation method and application - Google Patents
A kind of multi-stage porous loading type nickel-based catalyst, preparation method and application Download PDFInfo
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- CN106000405B CN106000405B CN201610316509.6A CN201610316509A CN106000405B CN 106000405 B CN106000405 B CN 106000405B CN 201610316509 A CN201610316509 A CN 201610316509A CN 106000405 B CN106000405 B CN 106000405B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 78
- 238000011068 loading method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000006057 reforming reaction Methods 0.000 claims abstract description 13
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 13
- 238000004939 coking Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 14
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 13
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 12
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000013528 metallic particle Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- 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
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
This application discloses a kind of multi-stage porous loading type nickel-based catalyst, preparation method and its applications in carbon dioxide methane reforming reaction.The multi-stage porous loading type nickel-based catalyst, including carrier and the active component being dispersed on carrier, it is characterized in that, the carrier is selected from least one of inorganic oxide, the carrier includes that average pore size is mesoporous for 1nm~50nm greater than the macropore of 50nm and average pore size；The active component is nickel.The multi-stage porous loading type nickel-based catalyst is used for carbon dioxide methane reforming reaction, has both excellent resistance to sintering and coking resistivity, has important practical significance to pushing methane reforming reaction by using carbon dioxide to industrialize.
Description
Technical field
It is anti-this application involves a kind of multi-stage porous loading type nickel-based catalyst, preparation method and its in carbon dioxide methane reforming
Application in answering, belongs to petrochemical industry.
Background technique
Coal, oil and natural gas are three macrofossil energy resources.Rich coal resources in China, but coal mining in recent years
With it is increasingly severe to the pollution of atmosphere, soil and groundwater during utilization, limit its and a large amount of use.And China's oil is stored up
Amount is few, it is necessary to rely on import, cause petroleum use cost higher.In recent years, before leaping to the world with China's shale gas ore reserves
Column, the development and utilization of natural gas are got more and more attention, and country has put into effect relevant policies and the comprehensive high-efficiency of natural gas is encouraged to utilize, day
Efficient utilize of right gas rises to national strategy level.Natural gas is other than can be directly as fuel, main component methane
It can be the chemical products with high added value via synthesis gas Efficient Conversion, such as produce ammonia, the methanol of large-tonnage demand, it can also
Produce the intermediate of the liquid fuels such as alkene, aromatic hydrocarbons.
Industrial production synthesis gas mainly uses natural gas for the method for raw material at present, mainly includes gas by partial oxidation of natural
Method and steam reforming.Gas by partial oxidation of natural method is a kind of method of relatively energy consumption, needs to consume a large amount of oxygen or air is made
For unstripped gas.If not using catalyst, reaction temperature is up to 1300~1400 DEG C.Even if using catalyst, catalytic bed temperature
900~1000 DEG C of Du Gaoyue and reaction need to carry out at high pressure (3.0MPa), require the high-temperature-resistant high-pressure-resistant of equipment severe
It carves.Reaction process maximum temperature is up to 1300 DEG C in natural gas intermittent conversion steaming process, and process consumes energy very much.Continuous steam conversion
Although energy consumption is relatively low, but still high-temperature and high-presure resistent more demanding to equipment.And either still continuous turn of intermittent conversion
Change, unstripped gas vapor influences whether the service life of equipment to the corrosion of equipment under the high temperature conditions, increases process costs.This
A little generally existing reaction temperatures of technical matters route are high, energy consumption is high, to the requirement of the high-temperature-resistant high-pressure-resistant of equipment resistance to vapor corrosion
The technical problems such as harshness.Therefore, the production of exploitation anhydrous and oxygen-free technique has great importance to the industrial production of synthesis gas.
Other than methane steam reformation, methane portion oxidation, methane carbon dioxide reformation is close gradually to be closed
The synthesis gas production technology approach of note.The advantage of methane carbon dioxide reformation route is as follows: (1) methane and carbon dioxide dry weight is had suffered
Cheng Wuxu oxygen and water, it is lower to equipment requirement.(2)H2/CO ratio is adjustable, is more suitable for subsequent F- T synthesis material rate；Reaction
It can be carried out at 650 DEG C or more, energy consumption is relatively low.(3) feed carbon dioxide is from a wealth of sources, cheap compared to oxygen.The technique mistake
Journey realizes carbon dioxide discharge-reduction while efficiently utilizing methane, has significant economic benefit and environmental benefit.Titanium dioxide
Carbon is coal and its final product that downstream product efficiently utilizes, and how to realize the regeneration of carbon dioxide, turning waste into wealth is
Coal Clean efficiently utilize in one of very important content.The process advan delays in the total amount for reducing carbon dioxide in atmosphere
Environmental pressure caused by greenhouse gases is solved, provides a kind of effective method for China's emission reduction.
Make inert methane and carbon dioxide molecule activation and be oriented conversion, exploitation has high activity, high selection
Property, high stability inexpensive catalyst be crucial.The active component of reforming methane with carbon dioxide catalyst is mainly VIII race's mistake
Metal is crossed, two class of noble metal catalyst and non-precious metal catalyst is divided into.The low and expensive unsuitable big rule of noble metal reserves
Mould industrial application, and measuring big inexpensive base metal then has apparent cost advantage.Especially nickel-base catalyst is considered as work
The best candidate of industry catalyst is studied by academia and industry extensively for many years.Although nickel-base catalyst is in carbon dioxide
Universal catalytic activity and selectivity with higher in reforming methane, but under the high temperature conditions easy-sintering, carbon deposit and inactivate, always
It is that the chemical industry route is hindered to realize industrialized key technology bottleneck.Therefore, the nickel-base catalyst of anti-carbon deposit and resistance to sintering is developed
To the process of industrialization for promoting the reaction of carbon dioxide methane dry reforming, realize that Resources of Carbon Dioxide is utilized with great environmental protection
Effect and economic benefit.
Mesoporous material is that a kind of important catalyst carrier, duct " interface confinement " effect help to prevent in catalysis reaction
Metallic particles carrier surface migration and grow up, the service life of industrial catalyst is effectively promoted.On the one hand, metal is living
Property center is located inside mesopore orbit, and nanoscale duct provides limited space metallic particles, and limits it into one
Agglomeration is walked, sintering of catalyst is prevented and inactivates.On the other hand, porous material usually has high-specific surface area, a large amount of gold
Category-carrier interface is conducive to enhance Metal-Support interaction, and then increases the stability of metallic particles.But tradition is mesoporous
The duct of carrier is very long, and duct internal resistance is made to become larger, and will be unfavorable for diffusion and mass transfer of the gas in duct, leads to carbon deposit shape
At.Chinese patent (CN104248959A) uses ordered mesoporous silica dioxide for carrier, passes through the dipping legal system of cyclo-dextrin-modified
For the nickel-base catalyst of neodymium doping, stability is on a declining curve in the long-time evaluation of methane reforming reaction by using carbon dioxide.
The nickel-base catalyst that some documents also report mesoporous material load has preferable stability, although can protect in a long time
Hold the conversion ratio of metastable carbon dioxide and methane；But react the transmission electron microscope after a period of time or TPO as the result is shown
Catalyst forms apparent carbon deposit, will seriously affect application (the ACS Catal.2012,2:1331- of catalyst longer time
1342；Energy&Environment Science2010,3:366-369；International Journal of
Hydrogen energy 2012,37:1454-14764).700 DEG C or more carbon deposits are mainly derived from reducing side reaction for methane.
To removing carbon, long life catalytic agent is obtained, it is necessary to improve to the structure of porous carrier, improve gas diffusion and biography
Matter rate makes methane decompose the C* generated and is reacted away in time by the O* that carbon dioxide decomposition generates.
Therefore, the porous carrier of novel structure is developed, the Ni-based load for having both excellent resistance to sintering and coking resistivity is obtained
Type catalyst has important practical significance to pushing methane reforming reaction by using carbon dioxide to industrialize.
Summary of the invention
According to the one aspect of the application, a kind of multi-stage porous loading type nickel-based catalyst is provided, to solve existing support type
Nickel-base catalyst in pyroreaction easy-sintering and carbon deposit and the problem of inactivate.
The multi-stage porous loading type nickel-based catalyst, including carrier and the active component being dispersed on carrier, feature exists
At least one of inorganic oxide is selected from, the carrier, and the carrier includes macropore and mesoporous；The active component is
Nickel.
The carrier includes the mesoporous and two distinct types of cellular structure of macropore.Compared to the single mesoporous load of tradition
Body, the mesopore orbit of the carrier facilitate the particle of fixed metal active constituent, and it is anti-in catalysis can be effectively prevented from metallic particles
It is sintered during answering because of migration.The diffusion and delivery rate of medium can be improved in macropore duct, effectively prevents carbon deposit
It is formed.The synergistic effect of multiple hole can solve high temperature sintering and carbon-collecting problem simultaneously, extend catalyst life.Therefore, have simultaneously
Standby mesoporous and macropore cellular structure inorganic oxide, can be used as in herein described multi-stage porous loading type nickel-based catalyst
Carrier, reach and solve high temperature sintering and carbon-collecting problem, extend the effect of catalyst life.Preferably, the carrier is selected from oxygen
Change at least one of aluminium, silica, titanium oxide, zirconium oxide.
Preferably, the average pore size of the macropore in the carrier is greater than 50nm, and mesoporous average pore size is 1nm~50nm.
It is further preferred that the average pore size of the macropore is 1 μm~2 μm；The mesoporous average pore size is 5nm~15nm.It is preferred that
Ground, the specific surface area of the carrier are 100m2/ g~350m2/g。
The particle diameter distribution of the active component nickel is narrow, is highly dispersed to be distributed in multi-stage porous carrier.Preferably, described point
The partial size for the active component nickel being dispersed on carrier is to be distributed between 5~100nm.It is further preferred that described be dispersed in carrier
On active component nickel the particle size range upper limit be selected from 30nm, 35nm, 40nm, 45nm, 50nm, lower limit be selected from 5nm, 10nm,
15nm.It is further preferred that the particle diameter distribution of the active component nickel being dispersed on carrier is between 10~30nm.
Mass percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst is 2%~10%；Institute
Mass percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst is stated with multi-stage porous loading type nickel-based catalyst
In the nickel element meter that contains.Preferably, quality percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst contains
Measure the upper limit be selected from 10%, 9%, 8%, 7%, 6%, 5%, 4.6%, 4.5%, 4.4%, lower limit be selected from 2%, 3%, 3.55%,
4%, 4.3%.It is further preferred that mass percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst
It is 3%~6%；Mass percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst is loaded with multi-stage porous
The nickel element meter contained in type nickel-base catalyst.
According to the another aspect of the application, the preparation method of above-mentioned multi-stage porous loading type nickel-based catalyst is provided.The side
Method is introduced ultrasonic link, is more advantageous to using ultrasonic assistant soakage-reduction method of improvement compared with traditional impregnation-reduction method
Diffusion of the dissolution and nickel element of nickel compound containing in multi-stage porous carrier duct, enhances load efficiency and Metal-Support is mutual
Effect.Before hydrogen reducing, catalyst roasts a period of time in air atmosphere, enhances the interaction between nickel and carrier.
The preparation method of any of the above-described multi-stage porous loading type nickel-based catalyst, which is characterized in that at least include the following steps:
A) carrier is placed in the solution containing nickel element, carries out ultrasonic immersing；
B) step a) obtained solid is after roasting in separation, vacuum drying, air and hydrogen reducing to get the multi-stage porous
Loading type nickel-based catalyst.
Preferably, ultrasonic immersing described in step a) is intermittent ultrasound, and total dip time is 24 hours~96 hours, is surpassed
The sound cumulative time is 2 hours~10 hours.It is further preferred that ultrasonic immersing described in step a) is intermittent ultrasound, it is total to soak
The stain time is 36 hours~60 hours, and the ultrasonic cumulative time is 2 hours~6 hours.It is further preferred that described in step a)
Ultrasonic immersing is intermittent ultrasound, and total dip time is 48 hours, and the ultrasonic cumulative time is 4 hours.
Those skilled in the art can select the supersonic frequency of intermittent ultrasound according to actual needs.Preferably, the ultrasound
Frequency is 20KHz~100Hz.
Solution described in step a) containing nickel element is obtained in a solvent by nickel compound containing dissolution.Preferably, described
Nickel compound containing is selected from least one of nickel acetate, nickel nitrate, nickel sulfate, nickel acetylacetonate；The solvent is selected from water, second
At least one of alcohol, acetone.
Those skilled in the art can select suitable impregnation ratio and nickel according to the amount for specifically needing nickel-loaded on catalyst
Concentration of element.Nickel element concentration in solution containing nickel element can be selected in 0.01mol/L between saturated solution.It is preferred that
Ground, the nickel element concentration in the solution containing nickel element are 0.1mol/L~1mol/L.It is further preferred that described contain
Nickel element concentration in the solution of nickel element is 0.25mol/L~0.75mol/L.Preferably, the use of the solution containing nickel element
Amount just floods carrier.
As an implementation, the step b) vacuum drying temperature is 60 DEG C~200 DEG C.Preferably, step b) institute
Stating vacuum drying is dried in vacuo 8 hours~10 hours at 60 DEG C~100 DEG C.It is further preferred that the step b) vacuum
Drying is dried in vacuo 8 hours~10 hours at 60 DEG C~100 DEG C.It is further preferred that the step b) vacuum drying
It is to be dried in vacuo 8 hours~10 hours at 80 DEG C.
As an implementation, roasting is with 1 DEG C/min~10 DEG C/min heating rate in the step b) air
By temperature from room temperature rise to 300 DEG C~800 DEG C between a certain temperature, roasting no less than 1 hour.Preferably, the step b) sky
In gas roasting be with 1 DEG C/min~5 DEG C/min heating rate by temperature from room temperature rise to 500 DEG C~700 DEG C between a certain temperature
Degree roasts 2 hours~4 hours.It is further preferred that roasting is incited somebody to action with the heating rate of 1 DEG C/min in the step b) air
Temperature rises to 600 DEG C from room temperature, roasts 2 hours~4 hours.
As an implementation, hydrogen reducing described in step b) is with 5 DEG C/min~20 DEG C/min heating rate
By temperature from room temperature rise to 600 DEG C~1000 DEG C between a certain temperature, in the mixture of hydrogen or hydrogen and non-active gas
Reduction no less than 1 hour；The flow velocity of the mixture of hydrogen or hydrogen and non-active gas is 20mL/min~80mL/min.It is preferred that
Ground, hydrogen reducing described in step b) be with 5 DEG C/min~15 DEG C/min heating rate by temperature from room temperature rise to 800 DEG C~
A certain temperature between 1000 DEG C, reduction no less than 1 hour~2 hours in hydrogen；The flow velocity of hydrogen is 20mL/min~40mL/
min.It is further preferred that hydrogen reducing described in step b) is to be risen to temperature from room temperature with the heating rate of 10 DEG C/min
900 DEG C, reduction no less than 1 hour~2 hours in hydrogen；The flow velocity of hydrogen is 20mL/min~40mL/min.It is described non-live
Property gas be selected from least one of nitrogen, inert gas.
According to the another aspect of the application, above-mentioned multi-stage porous loading type nickel-based catalyst is provided in reforming methane with carbon dioxide
Application in reaction, i.e., above-mentioned multi-stage porous loading type nickel-based catalyst are used for the side of carbon dioxide methane reforming reaction preparing synthetic gas
Method.The multi-stage porous loading type nickel-based catalyst is not for occurring sintering and carbon deposit, performance in methane reforming reaction by using carbon dioxide
Excellent high-temperature stability out can be used for manufacturing synthesis gas, realize carbon dioxide discharge-reduction and regeneration.
The method of the carbon dioxide methane reforming reaction preparing synthetic gas, which is characterized in that described to contain methane and dioxy
The raw material for changing carbon is contacted with catalyst, prepares synthesis gas；
Any of the above-described multi-stage porous loading type nickel-based catalyst of the catalyst, be prepared according to any of the above-described method it is more
At least one of grade hole loading type nickel-based catalyst.
Preferably, the raw material containing methane and carbon dioxide is in 600 DEG C of reaction temperature~850 DEG C, reaction pressure
It is contacted under conditions of 0.1MPa~0.5MPa with the catalyst, prepares synthesis gas；
The molar ratio of methane and carbon dioxide in the unstripped gas are as follows:
Methane: carbon dioxide=0.5~2.
Preferably, the carbon dioxide methane reforming reaction preparing synthetic gas carries out in using fixed bed reactors.
The beneficial effect of the application includes but is not limited to:
(1) multi-stage porous loading type nickel-based catalyst provided herein is more using having compared with conventional mesoporous supports
The carrier in grade duct；Multi-stage porous carrier introduces macropore duct, increases diffusion and the mass transfer rate of medium.The collaboration of multi-stage porous
Effect makes herein described catalyst in high-temperature catalytic reaction while having good anti-sintering and coking resistivity.
(2) method for preparing catalyst provided herein, using ultrasonic assistant soakage-reduction method of improvement.With tradition
Impregnation-reduction method compare, introduce ultrasonic link, the dissolution for being more advantageous to nickel salt and nickel element are in multi-stage porous carrier duct
Diffusion enhances load efficiency and Metal-Support interaction.Before hydrogen reducing, when catalyst roasts one section in air atmosphere
Between, enhance the interaction between ion and carrier.
(3) multi-stage porous loading type nickel-based catalyst provided by the present application, the high temperature as methane reforming reaction by using carbon dioxide
Rugged catalyst can manufacture synthesis gas, realize carbon dioxide discharge-reduction and regeneration.It is more under normal pressure, 800 DEG C of reaction conditions
The nickel-base catalyst of grade porous aluminum oxide load has both excellent anti-carbon deposit and sintering resistance energy, and catalyst life is long, the reaction time
In 100 hours, the conversion ratio of carbon dioxide and methane remains unchanged substantially.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of carrier multi-stage porous aluminum oxide micro-sphere section employed in embodiment 1；It (a) is to put
Big 1100 times of stereoscan photograph；It (b) is the scanning electron microscope (SEM) photograph for amplifying 35000 times.
Fig. 2 is the chromatography testing result that sample CAT-1 is used for methane reforming reaction by using carbon dioxide product in embodiment 2；(a)
It is the result of thermal conductivity detector (TCD) TCD；It (b) is flame ionization detector FID result.
Fig. 3 is the stability test result of 3 sample CAT-1 of embodiment.
Fig. 4 is the transmission electron microscope photo of 3 sample CAT-1 of embodiment reaction front and back；It (a) is the saturating of sample CAT-1 before reacting
Penetrate electromicroscopic photograph；(b) transmission electron microscope photo after to be sample CAT-1 react 102 hours at 800 DEG C.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless specifically stated otherwise, reagent used in the present embodiment and raw material can be bought by commercial sources.
In embodiment, the stereoscan photograph of sample is acquired using Hitachi, Japan S4800 type scanning electron microscope；Sample
Transmission electron microscope photo acquired on the F20 type transmission electron microscope of FEI Co..
In embodiment, carrier multi-stage porous aluminum oxide micro-sphere comes from husky rope (Sasol) company, specific surface area 197.91m2/
g；Macropore average pore size is 1.52 μm；Mesoporous average pore size is 9.80nm.The scanning electron microscope of multi-stage porous aluminum oxide micro-sphere section is shone
Piece is as shown in Figure 1, it can be seen that multi-stage porous aluminium oxide has macropore and mesoporous two different ducts.
In embodiment, the Ultrasound Instrument used in ultrasonic immersing is the KQ300ED of Kunshan Ultrasonic Instruments Co., Ltd.'s production
Type.
In embodiment, the load capacity using plasma emission spectrum (ICP) of nickel is public in French HORIBA JY on catalyst
Measurement is analyzed on the 2 type instrument of Ultima of department.
In embodiment, the reaction product of carbon dioxide methane reforming reaction preparing synthetic gas is detected in Shimadzu GC-2014 type color
It is carried out on spectrometer (TDX-01 column).
The preparation and characterization of 1 catalyst sample CAT-1~CAT-11 of embodiment
It takes a certain amount of nickel salt to be dissolved in wiring solution-forming in 10ml ethyl alcohol, is added 5g multistage porous aluminum oxide, one section of ultrasonic immersing
After time, it is filtered to remove solvent and extra unabsorbed nickel salt.The aluminium oxide for having adsorbed nickel ion is dried in vacuo at 80 DEG C
It after 8h, is roasted in air atmosphere, last hydrogen reducing, obtains the multi-stage porous loading type nickel-based catalyst.
Nickel content on the multi-stage porous loading type nickel-based catalyst is measured using ICP.It is observed using transmission scanning electron microscope
The particle size range of nickel particle on multi-stage porous loading type nickel-based catalyst.
Sample number into spectrum contains with the quality percentage of specific experiment parameter, nickel element in multi-stage porous loading type nickel-based catalyst
Amount, see Table 1 for details for the relationship of the particle size range of nickel particle.
Table 1
The evaluation of 2 catalyst reaction of embodiment
It takes 0.2g catalyst sample CAT-1 to be placed in the fixed bed reactors of internal diameter 1cm, carries out hydrogen after line reduction,
Adjust the temperature to reaction temperature.Gas is switched to CO2And CH4Gaseous mixture, N2For internal standard.Gas enters after cooling after reaction
Each material concentration of gas chromatographic detection calculates CO2And CH4Conversion ratio.
Reaction condition and CO2And CH4The relationship of conversion ratio is as shown in table 2.
When reaction condition is A, the chromatography testing result of reaction end gas is as shown in Figure 2.As seen from the figure, the application is mentioned
Had good selectivity for multi-stage porous loading type nickel-based catalyst, in product be essentially synthesis gas main component: hydrogen and
Carbon monoxide.
Table 2
CO2And CH4Conversion ratio use following equation to calculate respectively:
F in formulaCO2,inAnd FCO2,outIt is CO in unstripped gas and reaction end gas2Volume shunt volume；FCH4,inAnd FCH4,outRespectively
It is CH in reactants and products4Volume shunt volume.
Under same reaction conditions, the reaction result of catalyst sample CAT-2~CAT-11 is similar with CAT-1, according to catalysis
The difference of agent preparation method, CO2And CH4Conversion ratio variation in ± 10% range.
The evaluation of 3 catalyst stability of embodiment
0.2g catalyst sample CAT-1 is taken to be placed in the fixed bed reactors of internal diameter 1cm, in the reaction condition A of embodiment 2
Under, catalyst stability evaluation is carried out, as a result as shown in Figure 3.As seen from Figure 3, multi-stage porous support type provided herein
Nickel-base catalyst has excellent stability under normal pressure, 800 DEG C of reaction conditions, in 100 hours reaction time, carbon dioxide
It remains unchanged substantially with the conversion ratio of methane.
The transmission electron microscope photo of catalyst sample CAT-1 reaction front and back is as shown in Figure 4.Fig. 4 (a) is sample CAT- before reacting
1 transmission electron microscope photo；Fig. 4 (b) is the transmission electron microscope photo after sample CAT-1 reacts 102 hours at 800 DEG C.It can be with by figure
Find out, the active component nickel particle on catalyst sample before the reaction after do not change substantially, there is no sintering；And
It is formed in 102 hours catalysts without carbon deposit.
Under same reaction conditions, the catalyst stability evaluation result and CAT-1 class of catalyst sample CAT-2~CAT-11
Seemingly, in 100 hours reaction time, the conversion ratio of carbon dioxide and methane remains unchanged substantially.Sample CAT-2~CAT-11 exists
800 DEG C reaction 102 hours after transmission electron microscope photo with react before comparing result, it is similar with CAT-1, nickel particle there is no
Sintering, catalyst is interior to be formed without carbon deposit.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (14)
1. the method for carbon dioxide methane reforming reaction preparing synthetic gas, which is characterized in that by the original containing methane and carbon dioxide
Material contacts under conditions of 600 DEG C~850 DEG C of reaction temperature, reaction pressure 0.1MPa~0.5MPa with catalyst, preparation synthesis
Gas；
The molar ratio of methane and carbon dioxide in unstripped gas are as follows:
Methane: carbon dioxide=0.5~2；
The catalyst is multi-stage porous loading type nickel-based catalyst；
The multi-stage porous loading type nickel-based catalyst, including carrier and the active component being dispersed on carrier, the carrier is selected from
At least one of inorganic oxide, the carrier include macropore and mesoporous；
The partial size of active component nickel is to be distributed between 5~100nm；
The average pore size of the macropore is greater than 50nm, and the mesoporous average pore size is 5nm~50nm.
2. the method according to claim 1, wherein the average pore size of the macropore is 1 μm~2 μm.
3. the method according to claim 1, wherein the mesoporous average pore size is 5nm~15nm.
4. the method according to claim 1, wherein the specific surface area of the carrier is 100m2/ g~350m2/g。
5. the method according to claim 1, wherein the partial size of active component nickel is 10~30nm.
6. the method according to claim 1, wherein the active component nickel is in the loading type nickel-based catalysis of multi-stage porous
Mass percentage in agent is 2%~10%；
Mass percentage of the active component nickel in multi-stage porous loading type nickel-based catalyst is loading type nickel-based with multi-stage porous
The nickel element meter contained in catalyst.
7. according to the method described in claim 6, it is characterized in that, the active component nickel is in the loading type nickel-based catalysis of multi-stage porous
Mass percentage in agent is 3%~6%.
8. the preparation method of the described in any item methods of claim 1 to 7, the multi-stage porous loading type nickel-based catalyst is at least wrapped
Include following steps:
A) carrier is placed in the solution containing nickel element, carries out ultrasonic immersing；
B) step a) obtained solid is after roasting in separation, vacuum drying, air and hydrogen reducing to get multi-stage porous load
Type nickel-base catalyst.
9. according to the method described in claim 8, it is characterized in that, ultrasonic immersing described in step a) is intermittent ultrasound, always
Dip time is for 24 hours~96h, and the ultrasonic cumulative time is 2h~10h.
10. according to the method described in claim 9, it is characterized in that, ultrasonic immersing described in step a) is intermittent ultrasound, always
Dip time is 36h~60h, and the ultrasonic cumulative time is 2h~6h.
11. according to the method described in claim 8, it is characterized in that, the step b) vacuum drying temperature is 60 DEG C~200
℃；
Roasting is that temperature is risen to 300 DEG C from room temperature with 1 DEG C/min~10 DEG C/min heating rate in the step b) air
A certain temperature between~800 DEG C, roasting are no less than 1h；
Hydrogen reducing described in step b) is that temperature is risen to 600 DEG C from room temperature with 5 DEG C/min~20 DEG C/min heating rate
A certain temperature between~1000 DEG C, reduction is no less than 1h in the mixture of hydrogen or hydrogen and non-active gas；Hydrogen or hydrogen
The flow velocity of the mixture of gas and non-active gas is 20mL/min~80mL/min；The non-active gas is selected from nitrogen, inertia
At least one of gas.
12. according to the method for claim 11, which is characterized in that the step b) vacuum drying is at 60 DEG C~100 DEG C
Lower vacuum drying 8h~10h.
13. according to the method for claim 11, which is characterized in that roasting is with 1 DEG C/min~5 in the step b) air
DEG C/heating rate of min by temperature from room temperature rise to 500 DEG C~700 DEG C between a certain temperature, roast 2h~4h.
14. according to the method for claim 11, which is characterized in that hydrogen reducing described in step b) be with 5 DEG C/min~
The heating rate of 15 DEG C/min by temperature from room temperature rise to 800 DEG C~1000 DEG C between a certain temperature, restored in hydrogen many
In 2h；The flow velocity of hydrogen is 20mL/min~40mL/min.
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| US16/300,120 US11104575B2 (en) | 2016-05-12 | 2017-03-15 | Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas |
| PCT/CN2017/076793 WO2017193696A1 (en) | 2016-05-12 | 2017-03-15 | Catalyst, preparation method therefor and application thereof in preparation of syngas |
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| CN106807375A (en) * | 2017-01-24 | 2017-06-09 | 中国科学院福建物质结构研究所 | A kind of catalyst, its preparation method and application |
| EP3456411A4 (en) * | 2016-05-12 | 2019-12-18 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Catalyst, preparation method therefor and application thereof in preparation of syngas |
| CN106799263B (en) * | 2017-03-03 | 2019-03-22 | 中国科学院上海高等研究院 | Multistage pore catalyst of a kind of high intensity for methane tri-reforming and preparation method thereof |
| CN107626314A (en) * | 2017-10-18 | 2018-01-26 | 太原理工大学 | A kind of preparation method of the mesoporous Ni-based methanation catalyst of rule |
| CN109663593B (en) * | 2019-01-14 | 2021-03-30 | 宁夏大学 | Double-hole nickel-based catalyst, preparation method thereof and application thereof in methane and carbon dioxide reforming reaction |
| CN110252363A (en) * | 2019-06-25 | 2019-09-20 | 北京三聚环保新材料股份有限公司 | A kind of Ni-based methanation catalyst and preparation method thereof and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
| CN113368859A (en) * | 2021-04-16 | 2021-09-10 | 华南理工大学 | Nickel-zirconium co-doped mesoporous silica material and preparation method and application thereof |
| CN114570372B (en) * | 2022-03-29 | 2023-06-09 | 中国石油大学(华东) | Methane carbon dioxide dry reforming nickel-based catalyst and preparation method and application thereof |
| CN116272945A (en) * | 2023-01-16 | 2023-06-23 | 山东理工大学 | Preparation method and application of acid-base carbon-based catalyst |
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