JP5961166B2 - 高活性水性ガスシフト触媒、その製造方法と利用 - Google Patents
高活性水性ガスシフト触媒、その製造方法と利用 Download PDFInfo
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- JP5961166B2 JP5961166B2 JP2013525407A JP2013525407A JP5961166B2 JP 5961166 B2 JP5961166 B2 JP 5961166B2 JP 2013525407 A JP2013525407 A JP 2013525407A JP 2013525407 A JP2013525407 A JP 2013525407A JP 5961166 B2 JP5961166 B2 JP 5961166B2
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- 239000003054 catalyst Substances 0.000 title claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 36
- 229910000510 noble metal Inorganic materials 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims description 26
- 150000001340 alkali metals Chemical class 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 22
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012876 carrier material Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000446 fuel Substances 0.000 description 10
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- 239000011734 sodium Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 7
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- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- HHUIAYDQMNHELC-UHFFFAOYSA-N [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O HHUIAYDQMNHELC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQMSOYAHMZLJC-UHFFFAOYSA-N [Cr].[Ti].[V] Chemical compound [Cr].[Ti].[V] XSQMSOYAHMZLJC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- -1 manganese, iron compounds Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical class [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/78—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 alkali- or alkaline earth metals
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- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
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- 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
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- 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
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- C01—INORGANIC CHEMISTRY
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- 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
- C01B2203/1064—Platinum group metal catalysts
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- C01B2203/1082—Composition of support materials
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- Y02P20/00—Technologies relating to chemical industry
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Description
CO+H2O→CO2+H2
CO+3H2→CH4+H2O
CO2+4H2→CH4+2H2O
あるいは、
上記少なくとも一種の貴金属、少なくとも一種のアルカリ金属及び/又はアルカリ土類金属及び/又は少なくとも一種のドーパントの一部または全部が溶液または分散液として担体材料に塗布され、この担体材料が残りの部分のこれら成分と混合される本発明の触媒の製造方法を提供する。
図:
図1は、測定方法を説明するものである。なお、このなかの略語は以下の意味を持つ:
A 反応器出口でのCOの量(ppm)
B メタン含量(ppm)
T 温度(℃)
MG1 350℃でのメタン含量(ppm)
MG2 450℃でのメタン含量(ppm)
本発明を以下の実施例により説明するが、これらの実施例はなんら制限を加えるものではない:
本発明の触媒と比較用の触媒を以下の方法で製造する:
本発明の触媒と比較用触媒は、触媒製造例に示されるようにして含浸により製造できる。
所要量の硝酸鉄を上記量の硝酸白金溶液中に溶解し、蒸留水でCe/Zr担体材料の吸水量が90%に相当する体積まで希釈する。これらの押出品を容器に入れ、循環させながら白金/硝酸鉄溶液で噴霧含浸させる。含浸後、押出品をさらに5分間循環させ、次いで乾燥、次いで焼成する。次の製造工程で、水酸化カリウム溶液を蒸留水で、得られたPt/Feドープ後の押出品の吸水量の90%に相当する体積まで希釈する。次いでこれらの押出品を連続循環させながら得られた希水酸化カリウム溶液で噴霧含浸させる。含浸後、押出品をもう一度さらに5分間循環させ、次いで乾燥、次いで焼成する。
焼成 500℃で2時間
製品の重量 1001.8g
最終ドーピング量 0.9gのPt/100gの触媒
0.2gのFe/100gの触媒
2.0gのK/100gの触媒
本発明の触媒と比較用触媒は、以下の触媒製造の例に示されるように、混練により製造できる。
蒸留水の総使用量:69ml(HNO3とPt/Fe溶液の希釈用の蒸留水を含む)
加圧圧力 :60bar
混練時間 :49分間
乾燥 :対流乾燥炉中200℃で4時間
焼成 :対流炉中500℃で2時間
ドーピング結果 :0.9gのPt/100gの触媒
:0.2gのFe/100gの触媒
:1.0gのK/100gの触媒
製造した触媒の適性を証明する、これらをシフト反応に使用する。試験は次のように行う:
1.触媒の取り付け:15mlの触媒(床)または8〜12ml(モノリスの体積)を反応器内に取り付ける、
2.触媒取り付け後、始動前に装置全体に空気漏れがないことを試験する、
3.220℃に加熱し、同時にH2とN2の1:1混合物を用いて触媒を還元する、
4.220℃の温度に到達後この温度を5分間維持し、次いで試験を開始する、
5.初期データを記録、
6.初期温度プログラム、 600分間で220℃から450℃に加熱(連続的)、
7.450℃で20分間維持、
8.600分間で450℃から220℃に冷却(連続的)
7質量%のCO、
7質量%のCO2、
33質量%のH2、
27質量%のN2、および
26質量%のH2O。
−加熱:対流炉、温度範囲が最高で600℃、
−温度測定、反応器の外側、
−ガス計量:質量流量調節器(ブルックス)
−水の計量:液体流量計
−COとCO2の測定器:ジーメンス・ウルトラマット23
−メタンの分析装置:J.U.M社製FID、3−300A型
−圧力調整:レコ圧力調整弁
−リンセイス36チャンネル記録計を経由してデータ保管
−データ評価:ソフトウェア
1.温度T1(第一の昇温開始時の最低CO含量での温度[℃])
2.温度T2(第二の昇温開始時の最低CO含量での温度 [℃])
3.温度が350℃でのメタン含量MG(ppm)
4.温度が450℃でのメタン含量MG2(ppm)
5.方法M(220から440℃への加熱、シェブロンなど)
本発明の触媒と比較のために製造した触媒の結果を下の表1に示す:
2)元素;量[質量%]を報告
3)I=含浸;K=混練
4)比較試験
Claims (9)
- 担体材料上に、触媒の総重量に対して0.1〜0.96質量%の量の少なくとも一種の貴金属と、1.0〜4.0質量%の量の少なくとも一種のアルカリ金属及び/又はアルカリ土類金属を含み、及び更に上記担体材料上にドーパントとして少なくともFeを触媒の総重量に対して0.01〜5質量%の量で含み、
上記貴金属が、Au、Pt、Pd、Rh及びこれらの混合物からなる群から選ばれる水性ガスシフト触媒。 - 上記アルカリ金属及び/又はアルカリ土類金属が、Li、Na、K、Rb、Cs、Mg、Ca、Sr、及びこれらの混合物からなる群から選ばれる請求項1に記載の水性ガスシフト触媒。
- 上記担体材料が少なくともCe及び/又はZrを含む請求項1又は2に記載の水性ガスシフト触媒。
- 上記担体材料がさらにLa及び/又はAlを含む請求項3に記載の水性ガスシフト触媒。
- Ptが貴金属として存在し、上記アルカリ金属及び/又はアルカリ土類金属がLi、Na、K、Rb、Cs、Mg、Ca、Sr、及びこれらの混合物から選ばれ、上記ドーパントがFeであり、Ce及び/又はZrを含む担体材料が存在する請求項1〜4のいずれか一項に記載の水性ガスシフト触媒。
- 上記少なくとも一種の貴金属が触媒の総重量に対して0.1〜0.96質量%の量で存在し、上記少なくとも一種のアルカリ金属及び/又はアルカリ土類金属が1.2〜4.0質量%の量で存在し、上記ドーパントとして少なくともFeが0.05〜2.5質量%の量で存在し、上記担体材料が少なくともCe及び/又はZrを含む請求項1〜5のいずれか一項に記載の水性ガスシフト触媒。
- 上記少なくとも一種の貴金属、上記少なくとも一種のアルカリ金属及び/又はアルカリ土類金属及び/又は上記ドーパントとして少なくともFeの一部が溶液または分散液の形で担体材料に塗布され、この担体材料が、前記溶液または分散液の形で塗布されずに残っている成分と混合されるか、
又は
上記少なくとも一種の貴金属、上記少なくとも一種のアルカリ金属及び/又はアルカリ土類金属及び/又は上記ドーパントとして少なくともFeの全てが、溶液または分散液の形で担体材料に塗布される請求項1〜6のいずれか一項に記載の水性ガスシフト触媒の製造方法。 - 請求項1〜6のいずれか一項に記載の触媒の、一酸化炭素と水を二酸化炭素と水素に変換するための使用方法。
- 少なくとも一酸化炭素と水を含む混合ガスを二酸化炭素と水素に変換する方法であって、請求項1〜6のいずれか一項に記載の触媒を用いる方法。
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AU2012397688B2 (en) * | 2012-12-28 | 2016-05-26 | Mitsubishi Heavy Industries Engineering, Ltd. | CO shift catalyst, CO shift reactor, and method for purifying gasification gas |
BR102016022962B1 (pt) * | 2016-10-03 | 2021-10-26 | Petróleo Brasileiro S.A. - Petrobras | Processo de preparação de um catalisador de ferro-cromo promovido com platina, e, catalisador composto de ferro-cromo promovido com platina |
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US4956330A (en) * | 1989-06-19 | 1990-09-11 | Phillips Petroleum Company | Catalyst composition for the oxidation of carbon monoxide |
US5830425A (en) | 1993-02-09 | 1998-11-03 | Sud-Chemie Ag | Chromium-free catalyst based on iron oxide for conversion of carbon monoxide |
DE4303715A1 (de) * | 1993-02-09 | 1994-08-11 | Sued Chemie Ag | Chromfreier Katalysator auf Basis Eisenoxid zur Konvertierung von Kohlenmonoxid |
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US6969505B2 (en) | 2002-08-15 | 2005-11-29 | Velocys, Inc. | Process for conducting an equilibrium limited chemical reaction in a single stage process channel |
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CA2511018A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Catalyst formulations for hydrogen generation |
CA2510999A1 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation |
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GB0402104D0 (en) | 2004-02-02 | 2004-03-03 | Johnson Matthey Plc | Water gas shift catalyst |
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US7238333B2 (en) * | 2004-03-18 | 2007-07-03 | General Motors Corporation | High activity water gas shift catalysts with no methane formation |
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