CN115282970B - Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof - Google Patents
Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof Download PDFInfo
- Publication number
- CN115282970B CN115282970B CN202210925831.4A CN202210925831A CN115282970B CN 115282970 B CN115282970 B CN 115282970B CN 202210925831 A CN202210925831 A CN 202210925831A CN 115282970 B CN115282970 B CN 115282970B
- Authority
- CN
- China
- Prior art keywords
- nickel
- based catalyst
- metal oxide
- pore
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 77
- 238000002407 reforming Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000012298 atmosphere Substances 0.000 claims abstract description 51
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000748 compression moulding Methods 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001994 activation Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 241000282326 Felis catus Species 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000002222 fluorine compounds Chemical group 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000006057 reforming reaction Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- -1 carbon alkane Chemical class 0.000 description 2
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OWQNOTOYTSUHNE-UHFFFAOYSA-N carbon dioxide methane Chemical compound C.C(=O)=O.C OWQNOTOYTSUHNE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- C01B2203/0238—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
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- 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 provides a nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming, and a preparation method and application thereof. The nickel-based catalyst comprises the following components in percentage by mass: nickel oxide 5-30%; 68 to 94.99 percent of carrier metal oxide; 0.01 to 2 percent of oxide of M element with oxide film structure; the M element is at least one selected from cerium, zirconium and aluminum. The preparation method comprises the following steps: 1) Mixing nickel-loaded carrier metal oxide powder with fluoride powder of M element and compression molding; 2) Aging, drying and pore-forming; 3) Performing fluoride sublimation-deposition of M element in an inert atmosphere; 4) And performing first cooling, and then switching to perform second cooling in the air atmosphere. The oxide film limiting structure of the nickel-based catalyst realizes high dispersion and high thermal stability of nickel active sites under the reaction working condition of 600-1200 ℃, effectively inhibits migration and agglomeration of nickel particles, and has high activity and high carbon deposit resistance.
Description
Technical Field
The invention relates to the technical field of industrial catalysis, in particular to a nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming, a preparation method and application thereof.
Background
Research has been carried out for over 30 years around carbon dioxide-low carbon alkane reforming technology at home and abroad, mainly to develop high-activity and high-stability noble metal catalysts and Ni-based catalysts. However, noble metal catalysts are expensive, the process cost is too high, and the economic benefits are basically not achieved. Therefore, in recent years, research on non-noble metal catalysts (mainly, catalyst systems mainly comprising Ni as a main active metal) has been mainstream, and research has focused mainly on the study of the anti-carbon deposition and anti-sintering properties of nickel-based catalysts under high-temperature and normal-pressure conditions. Among them, the methane-steam reforming catalyst has been studied most, and the carbon dioxide-lower alkane reforming related art has been studied less.
The university of petroleum (Beijing) reports that it will produce CH in coke oven gas 4 With CO 2 Technology for reforming reaction, active components in developed nickel-based catalyst realize atomic scale dispersion, and added auxiliary agent has the function of strengthening CO 2 The adsorption, activation and conversion functions ensure that the nickel-based catalyst operates with high activity at high temperatures, but this technology has not been patented. Japanese Qiandao chemical construction Co., ltd disclose CO thereof 2 The reforming technology, related patent mainly has CN201780002255, etc., disclose the preparation of magnesia ball carrier coated with calcium oxide layer and catalyst preparation method using ruthenium or/and rhodium as active component, this technology adopts ruthenium or/and rhodium as active component, the cost is high. Patent CN99107321.5 discloses a nickel-based catalyst for preparing synthesis gas by reforming carbon dioxide-methane, which is prepared by impregnating superfine zirconia powder into nickel nitrate solution with a certain concentration, evaporating, drying and roasting, and is characterized in that the superfine zirconia powder is prepared by taking zirconium oxychloride as a precursor, taking diluted ammonia water as a precipitator, obtaining hydrogel, replacing the hydrogel with absolute ethyl alcohol, and introducing nitrogen into an autoclave. Patent CN200910154283.4 discloses that rare earth metal Nd and active metal component Ni are sequentially loaded on a carrier by adopting a beta-cyclodextrin modified impregnation method with Nd as an auxiliary agent, ni as an active component and ordered mesoporous silica (SBA-15) as a carrier, so as to prepare a rare earth metal Nd modified Ni/Nd/SBA-15 catalyst, and the catalyst can only operate under normal pressure, and the collapse of the molecular sieve carrier can be caused by excessive temperature and system pressure. Patent CN200810117478.7 discloses that gamma-Al 2 O 3 Or NiAl 2 O 4 As a carrier, ni as an active ingredientThe catalyst with a small amount of Pt as an auxiliary agent is applied to methane carbon dioxide reforming reaction, and the Pt is noble metal, has limited resources and high price, and limits the wide application prospect in industry. Patent CN201310581082.9 discloses that mesoporous oxide with high temperature stability, the inner surface of which is modified by alcoholic hydroxyl groups, is used as a carrier, and precursor salt of nickel is conveyed into the mesoporous pore canal under the stirring condition to obtain a dry reforming catalyst with good nickel dispersity; the method is characterized in that alcohol is used as a transport carrier, a nickel precursor is transported into a mesoporous pore canal of the carrier, the modification effect of an alcohol hydroxyl group on the inner wall of the pore canal of the carrier can control the size of nickel species in a smaller range, so that uniformly dispersed nickel oxide nano particles with small size are prepared and fixed in the mesoporous pore canal, a carbon template formed by the alcohol in the calcining process can also prevent the nickel species from migrating from the inside of the pore canal to the outer surface, and the height Wen Tuanju of nickel oxide is further inhibited; the catalyst prepared by the method can cause collapse of the carrier with a mesoporous structure under the conditions of excessive temperature and system pressure. Patent CN201710480165.7 discloses that by using trimethylaluminum and water as reaction sources, a substrate is made of K9 glass and JGSl quartz glass, and Ni/gamma-Al is prepared by an atomic deposition precipitation method in an immersion method 2 O 3 Depositing 1-100 layers of inert gamma-Al on the surface of the supported catalyst 2 O 3 Thin film, preparation of gamma-Al 2 O 3 /Ni/γ-Al 2 O 3 A sandwich structured catalyst; preparation of gamma-Al by the above-mentioned method 2 O 3 /Ni/γ-Al 2 O 3 The sandwich catalyst can only process powder samples, the atomic deposition precipitation method has extremely high requirements on processing equipment and high process cost, and gamma-Al is used under the severe working conditions of high temperature and high gas velocity of 800-1100 ℃ in industry 2 O 3 /Ni/γ-Al 2 O 3 Gamma-Al in sandwich structure 2 O 3 Will rapidly phase-convert to alpha-Al 2 O 3 Thereby causing collapse and destruction of the sandwich structure. Patent CN201710480366.7 discloses a NiCo/SiO prepared from organosilicon, organonickel, organocobalt and organic activator 2 The method utilizes porous silicon oxide to wrap NiCo alloy nano particles to inhibit NiCThe agglomeration and sintering behavior of the o-alloy nano particles can not meet the requirements of the industry under the severe working conditions of high temperature of 800-1200 ℃ and high gas velocity, and the powder catalyst containing the silicon oxide component can not meet the requirements of the industry on the mechanical strength of the reforming catalyst.
Based on the analysis, the research reports of the technology for preparing the synthesis gas by dry reforming of the low-carbon alkane at home and abroad are basically concentrated on laboratory and small-scale pilot-scale related work, and the higher activity and long-range stability of the catalyst are generally realized by improving the nickel loading capacity in order to meet the requirements in industry, so that the carbon deposition resistance of the catalyst is sacrificed, the service temperature of the catalyst, especially the dry reforming catalyst, is difficult to be reduced to below 600 ℃, the higher reaction temperature is extremely easy to cause unstable catalyst structure, active site sintering agglomeration and component loss, the prepared catalyst raw powder is required to have good catalytic performance, the carrier structure stability, the forming process and the mechanical strength of the catalyst raw powder are required to meet the industrial requirements, and therefore, the development of the nickel-based catalyst with high activity and high thermal stability and space-limited microstructure is particularly critical.
Disclosure of Invention
The invention provides a nickel-based catalyst for dry reforming of low-carbon alkane with oxide film limited field, and a preparation method and application thereof, aiming at solving the problems of rapid reduction of activity and carbon deposition caused by large nickel particle length on the surface of the catalyst due to unstable catalyst structure, extremely easy sintering agglomeration of surface active sites and component loss of the low-carbon alkane dry reforming catalyst under the working conditions of high temperature (600 ℃ -1200 ℃), and the like.
To achieve the above and other related objects, the first aspect of the present invention provides a nickel-based catalyst for dry reforming of oxide film limited-area light alkane, comprising the following components in percentage by mass:
nickel oxide 5-30%, such as 5-5.61%, 5.61-12.85%, 12.85-28.97% or 28.97-30%;
68 to 94.99 percent of carrier metal oxide, such as 68 to 69.24 percent, 69.24 to 86.02 percent, 86.02 to 93.82 percent or 93.82 to 94.99 percent;
0.01 to 2%, such as 0.01 to 0.57%, 0.57 to 1.13%, 1.13 to 1.79% or 1.79 to 2%, of an M element oxide having an oxide film structure;
the M element is at least one selected from cerium, zirconium and aluminum.
Preferably, the support metal oxide is selected from at least one of magnesium oxide, zirconium oxide and aluminum oxide.
The second aspect of the present invention provides a method for preparing the above nickel-based catalyst, comprising the steps of:
1) Mixing nickel-loaded carrier metal oxide powder with fluoride powder of M element and compression molding to obtain a molding precursor;
compression molding to obtain molded precursors meeting industrial requirements, such as Raschig rings, porous shapes, and the like;
2) Aging, drying and pore-forming the molding precursor in a dry air atmosphere to obtain a pore-forming material;
3) Performing sublimation-deposition of fluoride of M element on the pore-forming material in inert atmosphere to obtain a deposition material;
4) And (3) performing first cooling on the deposition material in an inert atmosphere, and then switching to air atmosphere containing water vapor for second cooling to obtain the nickel-based catalyst.
The fluoride of M element deposited on the inner wall of the pore canal reacts with water vapor in the air atmosphere to form a corresponding oxide film.
Preferably, the method further comprises at least one of the following technical characteristics:
11 In step 1), the granularity range of the nickel-loaded carrier metal oxide powder is 1-200 microns;
12 In the step 1), the mass ratio of nickel to carrier metal oxide in the nickel-loaded carrier metal oxide powder is 0.05-0.5: 1, such as 0.05 to 0.11: 1. 0.11 to 0.32:1 or 0.32 to 0.5:1, a step of;
13 In step 1), the nickel-supported carrier metal oxide powder is obtained by a preparation method comprising the following steps: dipping an aqueous solution containing a nickel source on a carrier metal oxide, and then drying, roasting, grinding and sieving;
14 In step 1), the granularity of the fluoride powder of the M element is 1-50 microns;
15 In the step 1), the mass ratio of the nickel-supported carrier metal oxide powder to the fluoride powder of the M element is 100:0.01 to 100:2, such as 100:0.01 to 100:0.44, 100:0.44 to 100:1.1, 100:1.1 to 100:1.73 or 100:1.73 to 100:2;
21 In step 2), the water vapor content in the dry air atmosphere is not more than 20g/m as dry gas 3 The method comprises the steps of carrying out a first treatment on the surface of the The dry air atmosphere may be obtained by dehydration treatment with a desiccant such as calcium chloride;
22 In step 2), the dry air atmosphere is a flowing air atmosphere;
23 In step 2), the aging temperature is room temperature, wherein the room temperature refers to the ambient temperature, such as 20-35 ℃;
24 In step 2), the aging time is 24 to 72 hours, such as 24 to 50 hours or 50 to 72 hours;
25 In step 2), aging until the side pressure strength of the formed precursor is more than 150N;
26 In step 2), the drying temperature is 100-150 ℃, such as 100-120 ℃ or 120-150 ℃;
27 In step 2), the drying time is 12-48 hours;
28 In the step 2), the temperature is increased to the pore-forming temperature at the heating rate of 2-20 ℃/min;
29 In step 2), the pore-forming temperature is 400-800 ℃;
210 In the step 2), the pore-forming time is 2-5 h;
31 In step 3), the dry air atmosphere is switched to inert atmosphere, such as high-purity nitrogen, high-purity argon and the like, wherein the high-purity refers to the volume concentration of the high-purity nitrogen is more than 99.9999%;
32 In step 3), the inert atmosphere is a static inert atmosphere, so that sublimated component loss is reduced and avoided;
33 In step 3), heating to 1400-1800 ℃ for sublimation-deposition;
34 In step 3), the sublimation-deposition time is 2-5 hours;
35 In the step 3), the deposition part is the inner wall of the pore canal for pore-forming;
36 In step 3), the sediment is a sediment precursor of the M element oxide film;
41 In step 3), the inert atmosphere is a static inert atmosphere;
42 In step 4), the temperature is reduced to 300-800 ℃, such as 300-400 ℃ or 400-800 ℃;
43 In step 4), the cooling rate of the first cooling is 10-20 ℃/min, such as 10-15 ℃/min or 15-20 ℃/min;
44 In step 4), the temperature is reduced to room temperature to 600 ℃;
45 In step 4), the second cooling rate is 10-20 ℃/min, such as 10-15 ℃/min or 15-20 ℃/min;
46 In step 4), the air atmosphere is a flowing air atmosphere;
47 In the step 4), the deposition precursor of the M element oxide film reacts with water vapor in the air atmosphere to generate the M element oxide film;
48 In step 4), the water vapor content in the air atmosphere is 80-200 g/m 3 Such as 80-130 g/m 3 Or 130-200 g/m 3 。
More preferably, at least one of the following technical features is further included:
111 In feature 11), the nickel-supported metal oxide powder has a particle size in the range of 5 to 100 microns;
131 In feature 13), the concentration of nickel in the aqueous solution comprising the nickel source is 0.2 to 4mol/L;
132 In feature 13), the carrier metal oxide has a particle size in the range of 1 to 200 microns;
133 In feature 13), the drying temperature is 100 to 150 ℃, such as 100 to 120 ℃ or 120 to 150 ℃;
134 In feature 13), the firing temperature is 500 to 1400 ℃, such as 500 to 600 ℃ or 600 to 1400 ℃;
135 In the feature 13), the roasting time is 1 to 6 hours;
141 In feature 14), the fluoride powder of element M has a particle size in the range of 1 to 10 microns.
Still more preferably, at least one of the following technical features is also included:
1111 In feature 111), the nickel-supported metal oxide powder has a particle size in the range of 10 to 40 microns;
1341 134) the firing temperature is 800-1300 ℃.
More preferably, at least one of the following technical features is further included:
291 In the 29), pore-forming temperature is 500-700 ℃;
2101 In feature 210), the pore-forming time is 3 to 5 hours.
More preferably, at least one of the following technical features is further included:
331 In the feature 33), the heating rate is 2-20 ℃/min;
332 In the feature 33), heating to 1400-1600 ℃ for sublimation-deposition;
341 In feature 34), the sublimation-deposition time is 3 to 5 hours.
In a third aspect, the invention provides the use of the nickel-based catalyst in the dry reforming of lower alkanes, such as the reforming of lower alkanes to produce synthesis gas, the reforming of lower alkanes to produce hydrogen by steam reforming, and the reforming of lower alkanes to carbon dioxide by steam mixing.
Preferably, the nickel-based catalyst is reduced and activated and then is subjected to low-carbon alkane dry reforming;
and/or, the lower alkane is reformed dry into lower alkane-carbon dioxide reformed, lower alkane-carbon dioxide-water vapor reformed or lower alkane-carbon dioxide-water vapor mixed reformed;
and/or the reaction pressure is 0.1-4 Mpa, such as 0.1-0.5 Mpa, 0.5-1.5 Mpa, 1.5-3 Mpa or 3-4 Mpa;
and/or the reaction temperature is 600-1200 ℃, such as 600-850 ℃, 850-950 ℃, 950-1150 ℃ or 1150-1200 ℃;
and/or, the reaction space velocity is 1000-150000 mL.g cat -1 ·h -1 Such as 1000-7443 mL.g cat -1 ·h -1 、7443～8747mL·g cat -1 ·h -1 Or 8747～150000mL·g cat -1 ·h -1 。
As described above, the invention has at least one of the following advantageous effects:
1) The nickel-based catalyst is suitable for a process for preparing synthesis gas by reforming low-carbon alkane-carbon dioxide by taking tail gas rich in low-carbon alkane, such as unconventional natural gas or coke oven gas, purge gas, flue gas and the like, and a process for preparing hydrogen by reforming low-carbon alkane-water vapor, a process for reforming low-carbon alkane-carbon dioxide-water vapor by mixing, and has flexible process operation and synthesis gas H 2 the/CO ratio is adjustable.
2) According to the preparation method, a pore structure rich in catalyst is obtained through pore formation, a deposition precursor of an M element oxide film is obtained through sublimation-deposition treatment of fluoride powder of an M element, then the deposition precursor of the M element oxide film is reacted with water vapor in an air atmosphere to obtain the nickel-based catalyst with an oxide film limiting structure, the physical isolation of nickel active sites on the surface of the catalyst after reduction and activation under industrial conditions is ensured by the oxide film limiting structure, and further high dispersion and high thermal stability of the nickel active sites under the reaction working condition of 600-1200 ℃ are realized, migration and agglomeration phenomena of nickel particles are effectively inhibited, and the catalyst is ensured to have high activity and high carbon deposition resistance.
3) The nickel-based catalyst is applicable to reaction pressure of 0.1-4 MPa, temperature of 600-1200 ℃ and airspeed of 1000-150000 mL g cat -1 h -1 Is a reaction condition of (2).
Drawings
FIG. 1 shows the cross section of the oxide film on the inner wall of the pore canal of the nickel-based catalyst in the oxide film limiting area before and after the reduction activation.
(a) Oxide membrane section of oxide membrane limiting area nickel-based catalyst pore inner wall before reduction activation.
(b) The microcosmic appearance I after the reduction and activation of the hydrogen/nitrogen mixed gas at 850 ℃.
(c) And (3) reducing and activating the mixed gas of hydrogen and nitrogen at 850 ℃ to obtain a second microstructure (nickel particles are encircled at the position).
FIG. 2 shows the furnace temperature of 850℃and the airspeed of 7443mL g cat -1 ·h -1 Reaction pressure 0.5MPa and raw material gas CH 4 /CO 2 The results of the dry reforming reaction of methane-dioxide were evaluated at a molar ratio of 1/1.
FIG. 3 shows the furnace temperature of 1150℃and the airspeed of 8747mL g cat -1 ·h -1 Reaction pressure 0.5MPa and raw material gas CH 4 /CO 2 /H 2 And evaluating the result of the methane-carbon dioxide-steam mixed reforming reaction under the condition of the O mole ratio of 1/1/0.2.
FIG. 4 shows the furnace temperature of 950 ℃ and the airspeed of 3929mL g cat -1 ·h -1 The reaction pressure is 1.5-3.0 MPa, and the raw material gas CH 4 /CO 2 The results of the methane-carbon dioxide dry reforming reaction were evaluated at a molar ratio of 1/1.7.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods and reagents not specifying the formulation in the following examples were carried out or configured under conventional conditions or conditions suggested by the manufacturer.
Example 1
Nickel-supported carrier metal oxide powder: 100g of magnesia powder with the granularity ranging from 10 to 40 micrometers is weighed, 20mL of nickel nitrate aqueous solution with the molar concentration of 4mol/L is added in a spraying way, fully kneaded by a high-speed mixer, dried for 2 hours at 120 ℃ and roasted for 3 hours at 500 ℃, fully ground and screened, and the powder with the granularity ranging from 10 to 40 micrometers is taken for standby.
Fluoride powder of M element: 0.5g of aluminum trifluoride powder, and the particle size range is 1-5 microns.
1) Fully mixing nickel-loaded magnesium oxide raw powder with the granularity ranging from 10 to 40 microns, aluminum fluoride powder with the granularity ranging from 1 to 5 microns and the like by a high-speed mixer, and then performing compression molding (Raschig ring shape) by a mechanical molding machine to obtain a molding precursor, wherein MgO: ni (NO) 3 ) 2 ：AlF 3 =100: 14.62:0.5 (mass ratio).
2) Aging at room temperature under dry flowing air atmosphere for 50 hr to obtain molded precursor with side pressure strength of above 150N, drying at 120deg.C for 12 hr, and transferring molded precursor toHeating to 400 ℃ at 20 ℃/min under a dry flowing air atmosphere for 5 hours at constant temperature to obtain a pore-forming material, wherein the dry flowing air atmosphere is that the water vapor content is not more than 20g/m based on dry gas 3 。
3) And after the constant-temperature pore-forming process at 400 ℃ is finished, introducing high-purity nitrogen to replace the air atmosphere in the furnace chamber, slowly heating to 1400 ℃ at 5 ℃/min, sealing the furnace chamber, maintaining the static high-purity nitrogen atmosphere and keeping the temperature for 3 hours, and performing fluoride sublimation/vaporization-deposition to obtain a deposited material.
4) Cooling the deposited material to 400 deg.C at a cooling rate of 10deg.C/min, stopping high purity nitrogen gas, and switching to flowing air (water vapor content 80 g/m) 3 ) Continuously cooling to room temperature at a cooling rate of 15 ℃/min to obtain a nickel-based catalyst: nickel oxide 5.61%, carrier magnesium oxide 93.82%, alumina with oxide film structure 0.57%.
The oxide film cross section of the inner wall of the pore canal of the nickel-based catalyst of the oxide film limit area before reduction and activation is shown in fig. 1 (a), and the inner surface of the catalyst is uniformly covered by a layer of alumina film with the thickness of about 200nm (namely, alumina with an oxide film structure) before reduction and activation. The microcosmic appearance after reduction and activation by 50% hydrogen/nitrogen mixed gas at 850 ℃ is shown in a figure 1 (b), a large number of nickel particles with the particle size smaller than 5nm are uniformly embedded on the surface of an oxide film after reduction and activation, and the obtained catalyst has special appearance before and after reduction and activation, effectively inhibits migration and agglomeration of the nickel particles, and has high activity and high thermal stability.
Single catalyst evaluation of Raschig ring catalyst particles prepared in steps 1) to 4) was carried out in a single tube apparatus with a loading of 100g, using 50% H at a furnace temperature of 850 ℃ 2 /N 2 In-situ reduction for 3 hours can be used for dry reforming reaction of methane-carbon dioxide, and the air speed is 7443cm at the furnace temperature of 850 DEG C 3 /(gh) is mL.g cat -1 ·h -1 Reaction pressure 0.5MPa and raw material gas CH 4 /CO 2 The performance of the catalyst was tested at a molar ratio of 1/1 and the results are shown in FIG. 2.
Example 2
Nickel-supported carrier metal oxide powder: weighing 100g of cerium oxide powder with the granularity range of 5-100 micrometers, spraying and adding 140mL of nickel nitrate aqueous solution with the molar concentration of 4mol/L, fully kneading by a high-speed mixer, drying at 120 ℃ for 2h, roasting at 600 ℃ for 3h, fully grinding and screening, and taking powder with the granularity range of 5-100 micrometers for later use.
Fluoride powder of M element: 3.5g of zirconium tetrafluoride powder, and the grain size range is 1-10 microns.
1) Fully mixing nickel-loaded cerium oxide raw powder with the granularity ranging from 5 to 100 microns, cerium fluoride powder with the granularity ranging from 1 to 10 microns and the like by a high-speed mixer, and then performing compression molding (Raschig ring shape) by a mechanical molding machine to obtain a molding precursor, wherein CeO: ni (NO) 3 ) 2 ：ZrF 4 =100: 102.31:3.5 (mass ratio).
2) Aging at room temperature for 50h under dry flowing air atmosphere with side pressure intensity of molding precursor above 150N, drying at 120deg.C for 12h, transferring molding precursor to high temperature furnace, heating to 800deg.C at 20deg.C/min under dry flowing air atmosphere for 5h, and making holes to obtain hole-forming material, wherein the water vapor content is not more than 20g/m 3 。
3) And after the constant-temperature pore-forming process at 800 ℃ is finished, introducing high-purity nitrogen to replace the air atmosphere in the furnace chamber, slowly heating to 1800 ℃ at 5 ℃/min, sealing the furnace chamber, maintaining the static high-purity nitrogen atmosphere and keeping the temperature for 3 hours, and performing fluoride sublimation/vaporization-deposition to obtain a deposited material.
4) Cooling the deposited material to 800 deg.c at 20 deg.c/min, stopping high purity nitrogen and switching to flowing air (130 g/m water vapor content) 3 ) Continuously cooling to room temperature at a cooling rate of 10 ℃/min to obtain a nickel-based catalyst: 28.97 percent of nickel oxide, 69.24 percent of carrier cerium oxide and 1.79 percent of cerium oxide with an oxide film structure.
The inner surface of the catalyst before reduction activation is uniformly covered by a zirconia film (i.e., zirconia having an oxide film structure). At 850℃with 50% H 2 /N 2 After the mixed gas is reduced and activated, a large number of nickel particles are uniformly embedded in oxygenThe catalyst obtained on the surface of the oxide film has special morphology before and after reduction and activation, effectively inhibits migration and agglomeration of nickel particles, and has high activity and high thermal stability.
Single catalyst evaluation of Raschig ring catalyst particles prepared in steps 1) to 4) was carried out in a single tube apparatus with a loading of 100g, using 50% H at a furnace temperature of 850 ℃ 2 /N 2 In-situ reduction for 3 hours can be used for methane-carbon dioxide-steam mixed reforming reaction at the furnace temperature of 1150 ℃ and the airspeed of 8747cm 3 /(gh) is mL.g cat -1 ·h -1 Reaction pressure 0.5MPa and raw material gas CH 4 /CO 2 /H 2 The performance of the catalyst was tested at an O molar ratio of 1/1/0.2 and the results are shown in FIG. 3.
Example 3
Nickel-supported carrier metal oxide powder: weighing 100g of alumina powder with the granularity of 5-100 micrometers, spraying and adding 100mL of nickel nitrate aqueous solution with the molar concentration of 2mol/L, fully kneading by a high-speed mixer, drying at 120 ℃ for 2h, roasting at 600 ℃ for 3h, fully grinding and screening, and taking powder with the granularity of 5-100 micrometers for later use.
Fluoride powder of M element: 1.5g cerium trifluoride powder with granularity ranging from 1 to 10 microns.
1) Fully mixing nickel-loaded alumina raw powder with the granularity ranging from 5 to 100 microns, aluminum fluoride powder with the granularity ranging from 1 to 10 microns and the like by a high-speed mixer, and then performing compression molding (Raschig ring shape) by a mechanical molding machine to obtain a molding precursor, wherein Al 2 O 3 ：Ni(NO 3 ) 2 ：CeF 3 =100: 36.54:1.5 (mass ratio).
2) Aging at room temperature for 50h in a dry flowing air atmosphere, wherein the side pressure intensity of the molding precursor is more than 150N, drying for 12h in a flowing drying air atmosphere at 120 ℃, transferring the molding precursor to a high-temperature furnace, heating to 800 ℃ at 20 ℃/min in the dry flowing air atmosphere, and maintaining the temperature for 5h at the same time, and fully pore-forming to obtain a pore-forming material, wherein the water vapor content of the dry flowing air atmosphere is not more than 20g/m based on dry gas 3 。
3) And after the constant-temperature pore-forming process at 800 ℃ is finished, introducing high-purity argon to replace the air atmosphere in the furnace chamber, slowly heating to 1800 ℃ at 5 ℃/min, sealing the furnace chamber, maintaining the static high-purity argon atmosphere and keeping the constant temperature for 3 hours, and performing fluoride sublimation/vaporization-deposition to obtain a deposited material.
4) Cooling the deposition material to 800 deg.C at 15 deg.C/min, stopping high purity argon gas, and switching to flowing air (water vapor content of 200 g/m) 3 ) Continuously cooling to room temperature at a cooling rate of 20 ℃/min to obtain a nickel-based catalyst: 12.85% of nickel oxide, 86.02% of carrier alumina and 1.13% of cerium oxide with an oxide film structure.
The inner surface of the catalyst before reduction activation is uniformly covered by a cerium oxide film (i.e., cerium oxide having an oxide film structure). At 850℃with 50% H 2 /N 2 After the mixed gas is reduced and activated, a large amount of nickel particles are uniformly embedded on the surface of the oxide film, and the obtained catalyst has special morphology before and after the reduction and activation, effectively inhibits migration and agglomeration of the nickel particles, and has high activity and high thermal stability.
Single catalyst evaluation of Raschig ring catalyst particles prepared in steps 1) to 4) was carried out in a single tube apparatus with a loading of 100g, using 50% H at a furnace temperature of 850 ℃ 2 /N 2 In-situ reduction for 3 hours can be used for dry reforming reaction of methane-carbon dioxide, and the air speed is 3929cm at the furnace temperature of 950 DEG C 3 /(gh) is mL.g cat -1 ·h -1 The reaction pressure is 1.5-3.0 Mpa (the reaction time is less than or equal to 24h, the reaction pressure is 1.5Mpa; the reaction time is more than 24h, the reaction pressure is 3 Mpa), the raw material gas CH 4 /CO 2 The performance of the catalyst was tested at a molar ratio of 1/1.7 and the results are shown in FIG. 4.
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. The preparation method of the nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming is characterized by comprising the following steps of:
mixing nickel-loaded carrier metal oxide powder with fluoride powder of M element and compression molding to obtain a molding precursor;
aging, drying and pore-forming the molding precursor in a dry air atmosphere to obtain a pore-forming material; the pore-forming temperature is 400-800 ℃;
performing sublimation-deposition of fluoride of M element on the pore-forming material in inert atmosphere to obtain a deposition material;
performing first cooling on the deposition material in an inert atmosphere, performing first cooling to 300-800 ℃, and then switching to air atmosphere containing water vapor for second cooling, wherein the second cooling is performed to room temperature-600 ℃ to obtain a nickel-based catalyst;
the nickel-based catalyst comprises the following components in percentage by mass:
nickel oxide 5-30%;
68-94.99% of carrier metal oxide;
0.01-2% of an oxide of an M element having an oxide film structure;
the M element is at least one selected from cerium, zirconium and aluminum.
2. The method of preparing a nickel-based catalyst according to claim 1, wherein the support metal oxide is selected from at least one of magnesium oxide, zirconium oxide, and aluminum oxide.
3. The method for preparing a nickel-based catalyst according to claim 1, further comprising at least one of the following technical features:
11 In the step 1), the granularity range of the nickel-loaded carrier metal oxide powder is 1-200 microns;
12 In the step 1), the mass ratio of the nickel-loaded carrier metal oxide powder to the carrier metal oxide is 0.05-0.5: 1, a step of;
13 In step 1), the nickel-supported carrier metal oxide powder is obtained by a preparation method comprising the following steps: dipping an aqueous solution containing a nickel source on a carrier metal oxide, and then drying, roasting, grinding and sieving;
14 In the step 1), the granularity range of the fluoride powder of the M element is 1-50 microns;
15 In the step 1), the mass ratio of the nickel-supported carrier metal oxide powder to the fluoride powder of the M element is 100: 0.01-100: 2;
21 In step 2), the water vapor content in the dry air atmosphere is not more than 20g/m as dry gas 3 ；
22 In step 2), the dry air atmosphere is a flowing air atmosphere;
23 In step 2), the aging temperature is room temperature;
24 In the step 2), the aging time is 24-72 hours;
25 In step 2), aging until the side pressure strength of the formed precursor is more than 150N;
26 In step 2), the drying temperature is 100-150 ℃;
27 In step 2), the drying time is 12-48 hours;
28 In the step 2), the temperature is increased to the pore-forming temperature at the heating rate of 2-20 ℃/min;
210 In the step 2), the pore-forming time is 2-5 h;
31 Step 3), switching the dry air atmosphere to an inert atmosphere;
32 In step 3), the inert atmosphere is a static inert atmosphere;
33 In step 3), heating to 1400-1800 ℃ for sublimation-deposition;
34 In step 3), the sublimation-deposition time is 2-5 hours;
35 In the step 3), the deposition part is the inner wall of the pore canal for pore-forming;
36 In step 3), the sediment is a sediment precursor of the M element oxide film;
41 In step 3), the inert atmosphere is a static inert atmosphere;
43 In the step 4), the cooling rate of the first cooling is 10-20 ℃/min;
45 In the step 4), the cooling rate of the second cooling is 10-20 ℃/min;
46 In step 4), the air atmosphere is a flowing air atmosphere;
47 In the step 4), the deposition precursor of the M element oxide film reacts with water vapor in the air atmosphere to generate the M element oxide film;
48 In step 4), the water vapor content in the air atmosphere is 80-200 g/m 3 。
4. The method for preparing a nickel-based catalyst according to claim 3, further comprising at least one of the following technical features:
111 In the feature 11), the particle size range of the nickel-supported metal oxide powder is 5-100 micrometers;
131 In the feature 13), the concentration of nickel in the aqueous solution containing the nickel source is 0.2 to 4mol/L;
132 In feature 13), the carrier metal oxide has a particle size in the range of 1 to 200 microns;
133 In the feature 13), the drying temperature is 100-150 ℃;
134 In the feature 13), the roasting temperature is 500-1400 ℃;
135 In the feature 13), the roasting time is 1-6 h;
141 In the feature 14), the particle size range of the fluoride powder of the M element is 1-10 μm.
5. The method for preparing a nickel-based catalyst according to claim 4, further comprising at least one of the following technical features:
1111 In feature 111), the nickel-supported metal oxide powder has a particle size range of 10-40 microns;
1341 134) the firing temperature is 800-1300 ℃.
6. The method for preparing a nickel-based catalyst according to claim 3, further comprising at least one of the following technical features:
291 In the step 2), the pore-forming temperature is 500-700 ℃;
2101 In feature 210), the pore-forming time is 3-5 hours.
7. The method for preparing a nickel-based catalyst according to claim 3, further comprising at least one of the following technical features:
331 In the feature 33), the heating rate is 2-20 ℃/min;
332 In the feature 33), heating to 1400-1600 ℃ for sublimation-deposition;
341 In feature 34), the sublimation-deposition time is 3-5 hours.
8. The nickel-based catalyst prepared by the preparation method of the nickel-based catalyst according to any one of claims 1 to 7.
9. Use of the nickel-based catalyst according to claim 8 in the dry reforming of light alkanes.
10. Use of the nickel-based catalyst according to claim 9, wherein the nickel-based catalyst is subjected to reduction activation and then to dry reforming of low-carbon alkanes;
and/or, the lower alkane is reformed dry into lower alkane-carbon dioxide reformed, lower alkane-carbon dioxide-water vapor reformed or lower alkane-carbon dioxide-water vapor mixed reformed;
and/or the reaction pressure is 0.1-4 MPa;
and/or the reaction temperature is 600-1200 ℃;
and/or the reaction space velocity is 1000-150000 mL·g cat −1 ·h −1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925831.4A CN115282970B (en) | 2022-08-03 | 2022-08-03 | Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210925831.4A CN115282970B (en) | 2022-08-03 | 2022-08-03 | Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115282970A CN115282970A (en) | 2022-11-04 |
| CN115282970B true CN115282970B (en) | 2023-12-08 |
Family
ID=83827124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210925831.4A Active CN115282970B (en) | 2022-08-03 | 2022-08-03 | Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115282970B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056633A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method of SiO2-coated core-shell structure catalyst |
| CN104841442A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of anti-carbon deposition mesoporous confinement methane dry reforming catalyst |
| KR20150129566A (en) * | 2014-05-12 | 2015-11-20 | 한국과학기술연구원 | Ni-based catalysts for combined steam and carbon dioxide reforming with natural gas |
| CN105688916A (en) * | 2016-02-23 | 2016-06-22 | 中国科学院上海高等研究院 | High-dispersion high-load high-activity nickel-based catalyst for low-temperature methane reforming and application of high-dispersion high-load high-activity nickel-based catalyst for low-temperature methane reforming |
| KR20180018999A (en) * | 2016-08-09 | 2018-02-22 | 주식회사 에코프로 | Ni-based catalyst for SMR reaction coated on metal foam with improved catalyst adhesion and reaction property, and Manufacturing method and Use thereof |
| CN109759074A (en) * | 2019-01-24 | 2019-05-17 | 浙江工业大学 | A kind of methane and carbon dioxide dry reforming nickel-base catalyst and its preparation method and application |
| CN110898839A (en) * | 2019-12-09 | 2020-03-24 | 大连理工大学 | Preparation method and application of supported anti-carbon deposition nickel-based catalyst |
| CN113000059A (en) * | 2021-02-04 | 2021-06-22 | 上海大学 | Nickel-based catalyst for dry reforming of methane and carbon dioxide and preparation method and application thereof |
-
2022
- 2022-08-03 CN CN202210925831.4A patent/CN115282970B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150129566A (en) * | 2014-05-12 | 2015-11-20 | 한국과학기술연구원 | Ni-based catalysts for combined steam and carbon dioxide reforming with natural gas |
| CN104056633A (en) * | 2014-06-18 | 2014-09-24 | 太原理工大学 | Preparation method of SiO2-coated core-shell structure catalyst |
| CN104841442A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of anti-carbon deposition mesoporous confinement methane dry reforming catalyst |
| CN105688916A (en) * | 2016-02-23 | 2016-06-22 | 中国科学院上海高等研究院 | High-dispersion high-load high-activity nickel-based catalyst for low-temperature methane reforming and application of high-dispersion high-load high-activity nickel-based catalyst for low-temperature methane reforming |
| KR20180018999A (en) * | 2016-08-09 | 2018-02-22 | 주식회사 에코프로 | Ni-based catalyst for SMR reaction coated on metal foam with improved catalyst adhesion and reaction property, and Manufacturing method and Use thereof |
| CN109759074A (en) * | 2019-01-24 | 2019-05-17 | 浙江工业大学 | A kind of methane and carbon dioxide dry reforming nickel-base catalyst and its preparation method and application |
| CN110898839A (en) * | 2019-12-09 | 2020-03-24 | 大连理工大学 | Preparation method and application of supported anti-carbon deposition nickel-based catalyst |
| CN113000059A (en) * | 2021-02-04 | 2021-06-22 | 上海大学 | Nickel-based catalyst for dry reforming of methane and carbon dioxide and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115282970A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dorling et al. | The structure and activity of supported metal catalysts: V. Variables in the preparation of platinum/silica catalysts | |
| KR100714663B1 (en) | A catalyst material and a process for its preparation | |
| JP4317706B2 (en) | Metal catalyst and method for preparing and using the same | |
| JP3999557B2 (en) | Catalyst for partial oxidation of hydrocarbon and method for producing hydrogen-containing gas using the catalyst | |
| JPH0480738B2 (en) | ||
| CN110898839A (en) | Preparation method and application of supported anti-carbon deposition nickel-based catalyst | |
| CN105771972A (en) | Preparing method of limited-range catalyst modified through atomic layer deposition and application thereof | |
| Phonthammachai et al. | Synthesis of high performance hydroxyapatite-gold catalysts for CO oxidation | |
| CN109718807B (en) | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming | |
| CN109718787B (en) | Cerium/yttrium stabilized zirconia support and catalyst | |
| CN108097244B (en) | Preparation of high-dispersion sintering-resistant supported ruthenium catalyst, catalyst and application | |
| CN113058632B (en) | Platinum-based catalyst with hexagonal boron carbon nitrogen as carrier and preparation method thereof | |
| CN114272927A (en) | Preparation method of zirconium dioxide modified layered porous vermiculite supported nickel-based catalyst | |
| KR20010101612A (en) | Catalyst Carrier Carrying Nickel Ruthenium and Lanthanum | |
| CN113209999B (en) | Catalyst for methane dry gas reforming reaction and preparation method thereof | |
| CN115282970B (en) | Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof | |
| US6562749B1 (en) | Process for the preparation of a catalyst or catalyst precursor | |
| CN110732335B (en) | Transition metal @ BO for methane dry gas reforming reactionxCore-shell structure nano catalyst and preparation method thereof | |
| EP4327937A1 (en) | Molded body of carbon dioxide methanation catalyst and method for producing the same | |
| CN110038563A (en) | A kind of charcoal@alumina load ruthenium-based ammonia synthetic catalyst and preparation method thereof | |
| JPH0459052A (en) | Catalyst for steam reforming | |
| JPH0729055B2 (en) | Catalyst for oxidizing carbon-containing compound and method for producing the same | |
| JP4298071B2 (en) | Exhaust gas purification material and method for producing the same | |
| KR102506775B1 (en) | Method for manufacturing exhaust gas purifying catalyst and the exhaust gas purifying catalyst therefrom | |
| López et al. | Support effect on Cu–Ru/SiO2 sol–gel catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |