EP3274088A1 - Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone - Google Patents
Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carboneInfo
- Publication number
- EP3274088A1 EP3274088A1 EP16714331.2A EP16714331A EP3274088A1 EP 3274088 A1 EP3274088 A1 EP 3274088A1 EP 16714331 A EP16714331 A EP 16714331A EP 3274088 A1 EP3274088 A1 EP 3274088A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalytically active
- active composition
- ruthenium
- weight
- catalyst
- 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.)
- Pending
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims description 35
- 239000003054 catalyst Substances 0.000 title abstract description 81
- GRLYPOPFNDQSKV-UHFFFAOYSA-N rhenium ruthenium Chemical compound [Ru].[Re] GRLYPOPFNDQSKV-UHFFFAOYSA-N 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 50
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 27
- 239000010948 rhodium Substances 0.000 claims abstract description 21
- 239000002019 doping agent Substances 0.000 claims abstract description 20
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000012876 carrier material Substances 0.000 claims abstract description 18
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 53
- 230000008569 process Effects 0.000 claims description 22
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- HLRPCWSWHIWFHM-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[O--].[Zr+4].[La+3].[Ce+3] HLRPCWSWHIWFHM-UHFFFAOYSA-N 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 20
- 230000002211 methanization Effects 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000012621 metal-organic framework Substances 0.000 description 12
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- -1 VIB transition metals Chemical class 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012013 faujasite Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 230000036316 preload Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010972 statistical evaluation Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- 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
- B01J23/75—Cobalt
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- 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
- B01J35/613—10-100 m2/g
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
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- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the invention relates to a catalytic composition and a process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing streams, in particular for use in fuel cell systems.
- PEM Polymer Electrolyte Membrane
- CO carbon monoxide
- a residual concentration of CO in the gas stream generally remains in the range of 0.25 to 1.5% by volume, depending on the process design and temperature.
- a CO removal can be achieved up to 2,500 ppm.
- the CO content in the hydrogen-rich gas must be further reduced in order to avoid poisoning of the anode catalyst; Guideline values are here between maximally 10 and 50 ppm.
- the CO methanation (hydrogenation of carbon monoxide to methane) is carried out according to the reaction equation:
- CO + 3H 2 -> CH 4 + H 2 0 ⁇ -206.2 kJ / mol
- the particular challenge for selective CO methanation is that CO should preferably be hydrogenated and not CO2, as this would consume more hydrogen.
- the CO concentration in the reformate is about 2500 ppm to 15,000 ppm, while the C0 2 content of about 15 to 25 vol .-% is an order of magnitude above the CO content. Accordingly, a CO-selective catalyst for the realization of low CO concentrations, as used for z. B. PEM fuel cells are required, indispensable.
- EP-A-1174486 combines a methanation stage with a selective oxidation unit for the purpose of lower oxygen consumption and lower CO 2 methanization rate.
- the catalyst used for the methanation contains Ru, Pt, Rh, Pd or Ni on an alumina carrier.
- WO 97/43207 describes the combination of a first stage for selective oxidation with a subsequent methanization stage with rhodium as the active component. With this combination, both processes can be operated under optimal conditions.
- EP-A-1246286 which includes a methanation reactor of a selective oxidation unit as a final process step of gas purification, for ease of construction and handling, employ conventional catalysts, predominantly ruthenium or nickel based.
- JP-A-2002/068707 deals with methanation catalysts supported on a refractory inorganic oxide selected from oxides of aluminum, titanium, silicon or zirconium.
- EP-A-1707261 describes a process for the selective oxidation of CO with a catalyst containing ruthenium on a support of mixed metal oxides doped with lanthanides.
- US Pat. No. 7,560,496 describes a process for the selective methanization of CO in the presence of CO.sub.2 using a catalyst comprising ruthenium, rhodium, nickel and / or cobalt as active component and at least one further dopant selected from the group consisting of iron, niobium, manganese, Molybdenum and zirconium on a carbon-based support material.
- WO 2008/101875 relates to a catalytically active composition for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing streams, which is characterized in that it contains ruthenium as the active component and a lanthanum-cerium-zirconium oxide as the carrier material.
- US-A-2005/009621 1 describes the selective methanization on a catalyst of Ru, Rh, Ni or combinations on ⁇ -zeolite, mordenite and faujasite. Although this achieves the desired CO concentrations below 100 ppm, the selectivity at temperatures above 190 ° C. at which the catalyst exhibits its activity drops markedly below 50%. Since the hydrogenation of CO2 per mole of 3/2 times as much hydrogen destroyed as the hydrogenation of CO, the demand for the highest possible selectivity is very important. In addition, a reasonable catalytic activity is achieved only over the very small temperature window between 170 ° C and 180 ° C.
- the object of the invention was therefore to provide a catalyst for selective CO methanation which obtains its selectivity and activity in a broad temperature range.
- a catalytically active composition which comprises ruthenium, rhodium, nickel, or cobalt or mixtures thereof as active component and rhenium as doping element contains a suitable carrier material.
- a catalyst containing ruthenium, rhodium, nickel or cobalt or mixtures thereof as active component and rhenium as doping element on a suitable support material is capable of methanating CO in a broad temperature range of about 100 to ensure 300 ° C in a nearly constant selectivity over a long period of time.
- Conventional catalysts show a significant drop in selectivity as the temperature and longer run times increase.
- a significantly lower control effort is required because the temperature window in the methanation of the CO must be kept less accurate.
- the invention thus provides a catalytically active composition for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, containing as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt and as a dopant rhenium on a support material.
- the catalytically active composition contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, preferably ruthenium.
- the active component is preferably present in the catalyst as an oxide.
- the actual active mass is then generated by activation with hydrogen in situ.
- An ex situ prereduction with eg hydrogen, forming gas or another suitable reducing agent is also possible.
- the active component of the catalyst is in metallic form. The catalyst can then be incorporated both in this form and after a subsequent surface passivation of the metallic component in the reactor.
- Suitable support materials are, according to the invention, all materials which can usually be used for this purpose in catalyst chemistry and which have a sufficiently high BET surface area and a corresponding porosity (pore volume).
- Examples include carrier materials selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB, VIB transition metals, oxides of rare earth metals, aluminosilicates, zeolites , MOFs (Metal Organic Framework) and their mixtures.
- Preferred supports according to the invention are those materials selected from the group consisting of Al 2 O 3, ZrO 2, T 2 O 2, and oxides of rare earth metals.
- a particularly preferred carrier material according to the invention is a lanthanum-cerium-zirconium oxide (LaCeZr oxide) having a lanthanum oxide content of from 0.1 to 15% by weight, preferably from 1 to 10% by weight and more preferably from 3 to 7% by weight .-% used.
- the cerium oxide content is 0.1 to 20 wt .-%, preferably 1 to 17 wt .-% and particularly preferably from 10 to 16 wt .-%, each based on the weight of the total support material.
- the zirconium oxide content of the support material is advantageously from 30 to 99.8 wt .-%.
- the carrier used according to the invention is characterized in that its physicochemical properties such as BET surface area, pore volume and lateral compressive strength have preferred values.
- the BET surface area of the support materials used for the catalysts according to the invention is at least 10 m 2 / g, advantageously at least 20 m 2 / g, preferably at least 40 m 2 / g, more preferably at least 60m 2 / g and all more preferably at least 80m 2 / g.
- the BET surface area is determined by a method according to DIN 66131.
- the pore volume of the carrier material is advantageously in the range from 0.05 to 1.5 cm 3 / g, preferably in the range from 0.1 to 1.0 cm 3 / g, particularly preferably in the range from 0.15 to 0.9 cm 3 / g, most preferably in the range of 0.17 to 0.7 cm 3 / g, in particular in Range of 0.2 to 0.6 cm 3 / g.
- the pore volume is determined by the method of mercury porosimetry according to DIN 66133.
- their compressive strength is advantageously at least 0.2 kgf, preferably at least 0.5 kgf, more preferably at least 1.0 kgf, most preferably at least 1.5 kgf, in particular at least 2.0 kgf.
- Side crush strength is a measure of the stability of a material when it exerts pressure on its side surfaces. The material is clamped between two punches (pre-load 0.5 N), which then move with 1, 6 mm / min test speed to each other and crush the material. The force needed to crush the material is recorded. Data result from a statistical evaluation of at least 20 moldings.
- the support material used according to the invention may contain, in addition to the components mentioned, further materials which can usually be used for this purpose in catalyst chemistry, for example alumina.
- Suitable binder materials are those which have a sufficiently high BET surface area.
- the BET surface area of these additionally used binder materials should be at least 120 m 2 / g.
- the content of these binder materials should not be 70% by weight, preferably 50% by weight, more preferably 30% by weight, and very particularly preferably 20% by weight, based in each case on the weight of the total support material exceed.
- the loading of the support material with at least one of the abovementioned active components according to the invention is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, more preferably 0.3 to 5% by weight, very particularly preferably 0.4 to 4.5 wt .-%, in particular 0.5 to 3 wt .-%. Further advantageous quantitative ranges are, for example, 0.1 to 10% by weight, 0.5 to 5% by weight and 0.7 to 4 and 1 to 3% by weight. The data are in each case based on the total weight of the catalytically active composition.
- the loading of the support material with rhenium as doping element is 0.01 to 20% by weight, preferably 0.05 to 10 wt .-%, particularly preferably 0.07 to 5 wt .-%, most preferably 0.08 to 4 Wt .-%, in particular 0.1 to 3 wt .-%.
- the data are in each case based on the total weight of the catalytically active composition.
- a preferred composition of the catalytically active system according to the invention contains 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-% rhenium and 0.1 to 20 wt.
- ruthenium based on the total weight of the catalytically active composition on a support selected from the group consisting of Al2O3, ZrÜ2, T1O2 and metal oxides of the rare earths, preferably on a support of ZrÜ2.
- Another preferred composition of the catalytically active system according to the invention contains 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-% rhenium and 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-% of ruthenium, based on the total weight of the catalytically active composition on a support selected from the group consisting of zeolite A. , ⁇ -zeolite, mordenite, faujasite, ZSM-5 and MOF.
- Another preferred composition of the catalytically active system comprises on a lanthanum-cerium-zirconia support having a lanthana content of 0.1 to 15% by weight and a ceria content of 0.1 to 20% by weight, respectively based on the weight of the total support material, 0.01 to 20 wt .-% rhenium and 0.1 to 20 wt .-% ruthenium, based on the total weight of the catalytically active composition.
- a further preferred composition of the catalytically active system comprises on a lanthanum-cerium-zirconium oxide support with a lanthanum oxide content of 0.1 to 15 wt.% And a cerium oxide content of 0.1 to 20 wt. , in each case based on the weight of the total support material, 0.05 to 10 wt .-% rhenium and 0.5 to 5 wt .-% ruthenium, based on the total weight of the catalytically active composition.
- Another preferred composition of the catalytically active system comprises on a lanthanum-cerium zirconia support having a lanthana content of 0.1 to 10% by weight and a ceria content of 0.1 to 7% by weight, respectively Based on the weight of the total support material, 0.07 to 5 wt .-% rhenium and 0.7 to 4 wt .-% ruthenium, based on the total weight of the catalytically active composition.
- a particularly preferred composition of the catalytically active system comprises on a lanthanum-cerium zirconia support having a lanthanum oxide content of 3 to 7 wt .-% and a ceria content of 10 to 16 wt .-%, each by weight of the total support material, 0.08 to 4 wt .-% rhenium and 1 to 3 wt .-% ruthenium, based on the total weight of the catalytically active composition.
- the catalyst according to the invention is characterized in that its physicochemical properties such as the phase composition by XRD, BET surface area, pore volume and lateral compressive strength have preferred values.
- the catalyst of the invention is characterized in that the recorded in 2 ⁇ (2 theta) range from 5 ° to 80 ° XRD diffraction at least the diffraction peaks at 26.54 ° 2 ⁇ (2 theta), 28.12 ° 2 ⁇ (2 theta), 29.90 ° 2 ⁇ (2 theta), 34.55 ° 2 ⁇ (2 theta), 49.70 ° 2 ⁇ (2 theta), 53.90 ° 2 ⁇ (2 theta), 59.12 ° 2 ⁇ (2 theta), 61, 96 ° 2 ⁇ (2 theta), 66.42 ° 2 ⁇ (2 theta), 73.48 ° 2 ⁇ (2 theta).
- the XRD analyzes were performed on a Bruker / AXS D8 Advance Series 2 using CuK alpha source (with a wavelength of 0.154 nm at 40 kV and 40 mA) and ⁇ - ⁇ geometry (Bragg-Brentano geometry). performed in reflection mode. The measurements were made over the measuring range: 5-80 ° (2 theta), 0.02 ° increments at 3.6 seconds / step.
- the catalyst according to the invention is characterized in that its BET surface area is at least 10 m 2 / g, advantageously at least 20 m 2 / g, preferably at least 40 m 2 / g, particularly preferably at least 60m 2 / g and most preferably at least 80m 2 / g.
- the BET surface area was determined according to DIN 66131.
- the catalyst according to the invention is characterized in that its pore volume advantageously in the range of 0.05 to 1, 5 cm 3 / g, preferably in the range of 0.1 to 1, 0 cm 3 / g, particularly preferably in Range of 0.15 to 0.9 cm 3 / g, most preferably in the range of 0.17 to 0.7 cm 3 / g, in particular in the range of 0.2 to 0.6 cm 3 / g.
- the method of mercury porosimetry according to DIN standard 66133 was used.
- the catalyst according to the invention is in the form of shaped articles (such as tablets, extrudates, spherical particles, etc.), the compressive strength of the shaped articles advantageously being at least 0.2 kgf, preferably at least 0.5 kgf, particularly preferably at least 1, 0 kgf, most preferably at least 1, 5 kgf, in particular at least 2.0 kgf.
- the lateral compressive strength is a measure of the stability of a material when it exerts pressure on its side surfaces. The material is clamped between two punches (pre-load 0.5 N), which then move with 1, 6 mm / min test speed to each other and crush the material. The force needed to crush the material is recorded. Data result from a statistical evaluation of at least 20 molded articles.
- the preparation of the catalyst used according to the invention is carried out in the usual manner, for example by the active component and optionally the doping element, preferably in the form of their salts / hydrates, brought into solution and then applied in a suitable manner, for example by impregnation on the support become. Thereafter, the catalyst is dried, calcined, optionally reduced and optionally passivated.
- the application of the active components by impregnation on the carrier material can be carried out in the usual manner, such. B. as a washcoat on a monolith. Implementation and process conditions are described, for example, in the Handbook of Heterogenous Catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, pages 57 to 66 and 147 to 149.
- An alternative method of preparation involves the kneading of the support materials with the salts / hydrates of the active and optionally doping elements with subsequent extrusion, drying and optionally calcination, optionally reduction and optionally passivation.
- the kneading of the carrier material with the active compounds and the further working steps can be carried out in the usual manner with known apparatuses.
- moldings from pulverulent raw materials can be carried out by customary methods known to the person skilled in the art, for example tableting, aggregation or extrusion, as described i.a. in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pages 414-417.
- auxiliaries known to the person skilled in the art such as binders, lubricants and / or solvents, may be added.
- the invention also provides the use of a catalytically active composition for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, which is characterized in that it comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and Cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB, VIB transition metals, oxides of metals rare earths, aluminosilicates, zeolites, MOFs (Metal Organic Framework) and mixtures thereof.
- ruthenium, rhodium, nickel and Cobalt preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al2O3, ZrÜ2, T1O2, SiC, Zn
- a preferred embodiment of the use according to the invention of the catalytically active composition for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which comprises as active component at least one element selected from the group consisting of Ruthenium, rhodium, nickel and cobalt, preferably ruthenium and containing rhenium as a dopant on a support material, wherein the total loading of the carrier material with the active component 0.1 to 20 wt .-% and with rhenium 0.01 to 20 wt .-%, each based on the total weight of the catalytically active composition, and the carrier material one or more components selected from the group consisting of Al 2 O 3, Zr 2 O, T 1 O 2, SiC, ZnO, Group IIA metals, Group HIB, IVB, VB, VIB transition metals, rare earth metal oxides, aluminosilicates, zeolites, MOFs (Metal
- a particularly preferred embodiment of the use according to the invention of the catalytically active composition for the selective methanation of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which comprises at least one element selected from the group as the active component of ruthenium, rhodium, nickel and cobalt, preferably ruthenium, and containing rhenium on a carrier material as doping agent, the total loading of the carrier material with the active component being 0.1 to 20% by weight, preferably 0.2 to 10% by weight.
- the support material preferably a component selected from the group consisting of zeolite A, ß-zeolite, Mordenite, faujasite, ZSM-5 and MOF.
- a catalytically active composition which comprises as active component at least one element selected from the group consisting of Ruthenium, rhodium, nickel and cobalt, preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.3 to 5 wt .-% and with rhenium 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-%, each based on the total weight of the catalytically active composition, and the support material preferably contains a lanthanum-cerium-zirconium oxide, wherein the support material
- the invention likewise provides a process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams, characterized in that a catalytically active composition is used which comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consisting of Al 2 O 3, ZrO 2, TIO 2, SiC, ZnO, Group IIA metals, Group HIB, IVB, VB, VIB oxides, transition metals, rare earth metal oxides, aluminosilicates, zeolites, MOFs (Metal Organic Framework) and mixtures thereof.
- a catalytically active composition which comprises as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium and as a dopant rhenium on a support material selected from the group consist
- a preferred embodiment of the process according to the invention for the selective methanization of carbon monoxide in hydrogen- and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which contains as active component at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt, preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, and with rhenium 0.01 to 20 wt .-%, each based on the total weight of the catalytically active composition, and the support material is one or more components selected from the group consisting of Al 2 O 3 , ZrO 2 , TiO 2 , SiC, ZnO, oxides of Group IIA metals, oxides of groups HIB, IVB, VB , VIB transition metals, oxides of rare earth metals, aluminosilicates, zeolites
- a particularly preferred embodiment of the process according to the invention for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing reformate streams is characterized in that a catalytically active composition is used which contains as active component at least one element selected from the group consisting of ruthenium, rhodium, Nickel and cobalt, preferably ruthenium, and containing rhenium on a carrier material as doping agent, the total loading of the carrier material with the active component being 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0, 3 to 5 wt .-% and with rhenium 0.01 to 20 wt .-%, preferably 0.07 to 5 wt .-%, particularly preferably 0.08 to 4 wt .-%, each based on the total weight of the catalytic active compound, and the support material preferably contains a component selected from the group consisting of zeolite A, ⁇ -zeolite, mordenite, faujasite, ZSM-5 and MOF
- a catalytically active composition which contains at least one element selected from the group consisting of ruthenium, rhodium, nickel and cobalt as the active component , preferably ruthenium and contains as a dopant rhenium on a support material, wherein the total loading of the support material with the active component 0.1 to 20 wt .-%, preferably 0.2 to 10% by weight, particularly preferably 0.3 to 5 wt.
- the support material preferably contains a lanthanum-cerium-zirconium oxide, wherein the support material comprises a lanthanum oxide Content of 0.1 to 15 wt .-%, a cerium oxide content of 0.1 to 20 wt .-% and a zirconium oxide content of 30 to 99.8 wt .-%, based on the weight of the total Carrier materials, contains.
- the selective methanation process according to the invention can be carried out in a temperature range of preferably 100 to 300 ° C.
- Particularly advantageous is the selective methanization of CO in a temperature range of 180 to 260 ° C.
- This temperature allows for direct thermal integration to the upstream cryogenic conversion. It is thus possible to couple the methanation stage according to the invention directly to the low-temperature conversion stage.
- the high activity with equally high CO selectivity in this temperature range ensures that a stable and above all thermally integrated operation of the catalyst becomes possible.
- the inventive method is operated in a mode of operation, the GHSV in a range of 200 to 20,000 r 1 , preferably in a range of 500 to
- the GHSV "gas hourly space velocity" is an indication of the gas flow of a reaction gas in liters per liter of catalyst and per hour at standard temperature and pressure.
- the novel process for the selective methanization of carbon monoxide in hydrogen and carbon dioxide-containing streams on the highly active methanation catalyst according to the invention is carried out in customary apparatuses and under customary conditions for carrying out a methanation reaction, as described, for example, in the Handbook of heterogeneous catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, page 353, and with overflow of the catalyst with a CO and hydrogen-containing process gas.
- the process gas suitable for the methanation process is a synthesis gas that can be generated by reforming solid, liquid and gaseous fuels.
- Preferred fuels include natural gas, LPG, long-chain hydrocarbons (gasoline, diesel) and alcohols such as methanol or ethanol.
- Reforming means the processes known to the person skilled in the art, such as steam reforming, partial oxidation and autothermal reforming.
- Preferred reforming processes include steam reforming and autothermal reforming of hydrocarbons such as natural gas, gasoline and diesel.
- the catalytically active composition is thus outstandingly suitable for CO fine cleaning in hydrogen and carbon dioxide-containing reformate streams, in particular for use in the production of hydrogen for fuel cell applications.
- the invention will be explained in more detail with reference to the following embodiments, but without thereby making a corresponding limitation.
- the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReG-4) and dried again at 120 ° C. for sixteen hours.
- the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 2% by weight of Re as a dopant.
- the BET surface area of the finished catalyst was 83 m 2 / g *) .
- the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
- HReC perrhenic acid solution
- the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 1 wt% Re as a dopant.
- the BET surface area of the finished catalyst was 86 m 2 / g *) .
- Example 3 148.1 g of a lanthanum-cerium-zirconium oxide support (containing 65% by weight of ZrO 2 , 15% by weight of CeO 2 , 5% by weight of La 2 C> 3 and 15% by weight of Al 2 O 3) were mixed with a 30% strength by weight RuC solution, the amount of which was adjusted so that the finished catalyst carried 2% by weight of Ru as the active composition. Subsequently, the impregnated support was dried in a rotary kiln at 120 ° C for sixteen hours and then calcined at 475 ° C for two hours (at a heating rate of 4 ° C / min).
- the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
- HReC perrhenic acid solution
- the concentration of perrhenic acid was adjusted so that the finished catalyst after drying contained 0.5 wt .-% Re as a dopant.
- the BET surface area of the finished catalyst was 85 m 2 / g *) .
- the ruthenium catalyst thus obtained was then impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C for sixteen hours.
- HReC perrhenic acid solution
- the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 0.25 wt% Re as a dopant.
- the BET surface area of the finished catalyst was 88 m 2 / g * >.
- the ruthenium catalyst thus obtained was subsequently impregnated with a perrhenic acid solution (HReC) and dried again at 120 ° C. for sixteen hours.
- HReC perrhenic acid solution
- the concentration of perrhenic acid was adjusted so that the final catalyst after drying contained 0.1 wt% Re as a dopant.
- the BET surface area of the finished catalyst was 86 m 2 / g *) . *)
- the BET surface area of the respective catalysts according to the invention was determined according to DIN 66131.
- Example 8 Selective methanation using the catalysts from Examples 1 to 7
- the catalyst mixture consisted of about 20 ml catalyst pellets (1, 5 x 1, 5 mm).
- the feed used was 5 ml of stea- tite spheres with a diameter of 1.8 to 2.2 mm, which filled the residual volume of the reactor.
- the catalyst was first reduced with 90 l / h of nitrogen and 10 l / h of hydrogen at 230 ° C for one hour.
- the gas composition chosen for the experiment is typical for the output of the low-temperature shift stage after the reforming of methane and was 22% by volume H 2 , 28% by volume N 2 , 25% by volume H 2 O, 13% by volume. % CO 2 , 5% CO by volume and 0.5% CH 4 by volume. All experiments were carried out at a pressure of 2 bara and a load of 5000 lh- 1 -
- the selectivity is the quotient of the amount of CO converted and the amount of methane produced (in% by volume).
- the turnover refers to CO.
- Example 1 2% by weight Ru / 2% by weight Re 83% 51%
- Example 2 2% by weight Ru / 1% by weight Re 84% 53%
- Example 3 2% by weight Ru / 0.5% by weight Re 82% 49%
- Example 4 2% by weight Ru / 0.25% by weight Re 80% 45%
- Example 5 2% by weight Ru / 0.1% by weight Re 82% 46%
- Rhenium doped ruthenium catalysts from Examples 1 to 5 significantly higher CO selectivities over the temperature range of 200 to 260 ° C than the two rhenium-free catalysts from Comparative Examples 6 and 7.
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Abstract
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EP15161099.5A EP3072589A1 (fr) | 2015-03-26 | 2015-03-26 | Catalyseur et procédé de méthanisation sélective de monoxyde de carbone |
PCT/EP2016/056418 WO2016151031A1 (fr) | 2015-03-26 | 2016-03-23 | Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone |
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EP3274088A1 true EP3274088A1 (fr) | 2018-01-31 |
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EP15161099.5A Withdrawn EP3072589A1 (fr) | 2015-03-26 | 2015-03-26 | Catalyseur et procédé de méthanisation sélective de monoxyde de carbone |
EP16714331.2A Pending EP3274088A1 (fr) | 2015-03-26 | 2016-03-23 | Catalyseur à base de ruthénium-rhénium et procédé de méthanisation sélective de monoxyde de carbone |
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US (1) | US10780422B2 (fr) |
EP (2) | EP3072589A1 (fr) |
JP (1) | JP6808638B2 (fr) |
KR (1) | KR102611732B1 (fr) |
CN (1) | CN107427819B (fr) |
CA (1) | CA2980254C (fr) |
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US11529618B2 (en) | 2016-11-28 | 2022-12-20 | Basf Se | Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins |
CN108543534B (zh) * | 2018-05-14 | 2020-12-15 | 中国矿业大学(北京) | 一种用于催化臭氧氧化的催化剂及其制备方法 |
KR102257706B1 (ko) * | 2020-02-24 | 2021-05-27 | 아주대학교산학협력단 | 바이오매스 기반 다공성 탄소 지지체 담지 금속 촉매, 이의 제조 방법 및 상기 촉매를 이용하여 퓨란으로부터 테트라하이드로퓨란을 제조하는 방법 |
KR102572816B1 (ko) * | 2022-07-15 | 2023-08-31 | (주)한빛레이저 | 산소 동위원소 농축수 제조용 촉매 및 상기 촉매를 이용한 산소 동위원소 농축수의 제조방법 |
CN117101673B (zh) * | 2023-06-19 | 2024-06-21 | 广东工业大学 | 一种Ni-Re双金属基催化剂及其制备方法和应用 |
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US3615164A (en) | 1968-01-10 | 1971-10-26 | Bernard S Baker | Process for selective removal by methanation of carbon monoxide from a mixture of gases containing carbon dioxide |
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US4567205A (en) * | 1984-06-29 | 1986-01-28 | Exxon Research And Engineering Co. | Ruthenium catalysts, and use thereof for Fischer-Tropsch synthesis |
EP0231401B1 (fr) * | 1984-06-29 | 1992-09-09 | Exxon Research And Engineering Company | Catalyseurs ruthénium rhénium oxyde de titane et leur utilisation pour des sythèses Fischer-Tropsch |
GB9609918D0 (en) | 1996-05-11 | 1996-07-17 | Johnson Matthey Plc | Hydrogen purification |
GB9620287D0 (en) | 1996-09-28 | 1996-11-13 | Johnson Matthey Plc | Carbon monoxide removal |
JP3865479B2 (ja) * | 1997-09-09 | 2007-01-10 | 大阪瓦斯株式会社 | 一酸化炭素除去システム及び一酸化炭素の除去方法 |
WO2000053696A1 (fr) | 1997-09-09 | 2000-09-14 | Osaka Gas Co., Ltd. | Systeme et procede de suppression du monoxyde de carbone |
JP4460126B2 (ja) | 2000-08-31 | 2010-05-12 | 出光興産株式会社 | 水素含有ガス中の一酸化炭素の除去方法 |
EP1246286A1 (fr) | 2001-03-31 | 2002-10-02 | OMG AG & Co. KG | Appareil combiné pour la production de chaleur et de courant avec système de production de gaz et piles à combustible et procédé de fonctionnement |
US20050096211A1 (en) | 2003-10-31 | 2005-05-05 | Hiroshi Takeda | Catalyst for the conversion of carbon monoxide |
US20050096212A1 (en) | 2003-10-31 | 2005-05-05 | Hiroshi Takeda | Catalyst for the conversion of carbon monoxide |
KR100903468B1 (ko) * | 2004-12-20 | 2009-06-18 | 다나까 기낀조꾸 고교 가부시끼가이샤 | 디젤 배기가스 처리용 연소촉매 및 디젤 배기가스의처리방법 |
DE102005003311A1 (de) | 2005-01-24 | 2006-07-27 | Basf Ag | Katalytisch aktive Zusammensetzung zur selektiven Methanisierung von Kohlenmonoxid und Verfahren zu deren Herstellung |
JP4824332B2 (ja) | 2005-03-29 | 2011-11-30 | エヌ・イーケムキャット株式会社 | 一酸化炭素除去用触媒 |
AR053588A1 (es) * | 2005-04-21 | 2007-05-09 | Shell Int Research | Catalizador de hidrogenacion y metodo de hidrogenacion |
JP5094028B2 (ja) * | 2006-03-20 | 2012-12-12 | 日揮触媒化成株式会社 | 一酸化炭素メタネーション用触媒および該触媒を用いた一酸化炭素のメタネーション方法 |
US8067332B2 (en) | 2006-05-03 | 2011-11-29 | Samsung Sdi Co., Ltd. | Methanation catalyst, and carbon monoxide removing system, fuel processor, and fuel cell including the same |
JPWO2008075761A1 (ja) | 2006-12-20 | 2010-04-15 | 新日本石油株式会社 | 一酸化炭素濃度を低減するための触媒 |
JP4864688B2 (ja) * | 2006-12-25 | 2012-02-01 | 日揮触媒化成株式会社 | 一酸化炭素メタネーション用触媒および該触媒を用いた一酸化炭素のメタネーション方法 |
WO2008101875A1 (fr) | 2007-02-23 | 2008-08-28 | Basf Se | Catalyseur et procédé de méthanisation sélective de monoxyde de carbone |
KR20090119766A (ko) * | 2007-03-13 | 2009-11-19 | 우미코레 아게 운트 코 카게 | 일산화탄소의 메탄화를 위한 촉매로서 금속 도핑된 니켈 산화물 |
CN102151570A (zh) * | 2011-03-01 | 2011-08-17 | 上海中科高等研究院 | 一种甲烷-二氧化碳重整反应催化剂及其制备方法 |
-
2015
- 2015-03-26 EP EP15161099.5A patent/EP3072589A1/fr not_active Withdrawn
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2016
- 2016-03-23 EP EP16714331.2A patent/EP3274088A1/fr active Pending
- 2016-03-23 CA CA2980254A patent/CA2980254C/fr active Active
- 2016-03-23 KR KR1020177030700A patent/KR102611732B1/ko active IP Right Grant
- 2016-03-23 JP JP2017550562A patent/JP6808638B2/ja active Active
- 2016-03-23 US US15/561,737 patent/US10780422B2/en active Active
- 2016-03-23 CN CN201680017984.1A patent/CN107427819B/zh active Active
- 2016-03-23 WO PCT/EP2016/056418 patent/WO2016151031A1/fr active Application Filing
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KR102611732B1 (ko) | 2023-12-07 |
EP3072589A1 (fr) | 2016-09-28 |
US20180085739A1 (en) | 2018-03-29 |
JP6808638B2 (ja) | 2021-01-06 |
JP2018514372A (ja) | 2018-06-07 |
CN107427819A (zh) | 2017-12-01 |
CN107427819B (zh) | 2021-08-24 |
CA2980254C (fr) | 2023-07-25 |
US10780422B2 (en) | 2020-09-22 |
CA2980254A1 (fr) | 2016-09-29 |
KR20170130561A (ko) | 2017-11-28 |
WO2016151031A1 (fr) | 2016-09-29 |
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