TWI495508B - Carbon monoxide conversion catalyst and the use of one of the carbon dioxide modification method - Google Patents
Carbon monoxide conversion catalyst and the use of one of the carbon dioxide modification method Download PDFInfo
- Publication number
- TWI495508B TWI495508B TW096138276A TW96138276A TWI495508B TW I495508 B TWI495508 B TW I495508B TW 096138276 A TW096138276 A TW 096138276A TW 96138276 A TW96138276 A TW 96138276A TW I495508 B TWI495508 B TW I495508B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- zinc
- copper
- oxide
- mass
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 121
- 238000006243 chemical reaction Methods 0.000 title claims description 49
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 20
- 238000002715 modification method Methods 0.000 title description 5
- 239000001569 carbon dioxide Substances 0.000 title description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000446 fuel Substances 0.000 claims description 40
- 239000011787 zinc oxide Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000005751 Copper oxide Substances 0.000 claims description 29
- 229910000431 copper oxide Inorganic materials 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000011029 spinel Substances 0.000 claims description 9
- 229910052596 spinel Inorganic materials 0.000 claims description 9
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 230000000694 effects Effects 0.000 description 24
- 238000011282 treatment Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- -1 copper-zinc-aluminum Chemical compound 0.000 description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000007731 hot pressing Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000002407 reforming Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910007572 Zn-K Inorganic materials 0.000 description 4
- 238000002453 autothermal reforming Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000006011 modification reaction Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 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 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- B01J23/76—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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- C01B3/06—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
-
- 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
-
- 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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/17—Copper
-
- 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
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/27—Zinc
-
- 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
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
-
- 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
-
- 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
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- 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
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- 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
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
本發明係有關一氧化碳轉化用觸媒及使用其一氧化碳的改性方法,特別有關氫製造觸媒及燃料電池用一氧化碳轉化用觸媒(以下,CO表示一氧化碳)。
近年來,由環境問題之新能量技術倍受矚目,作為此一新能量技術之燃料電池極為醒目。此燃料電池係使氫與氧藉由電化學性反應,將化學能量轉化為電能量,其能量之利用效率高,作為民生用,產業用或汽車用等,被廣泛,且積極進行實用化之研究。
燃料電池中,因應所使用之電解質種類,公知者有磷酸型、熔融碳酸鹽型、固體氧化物型、固體高分子型等形態。作為製造此等燃料電池用之氫的氫源者,有以甲烷為主體之液化天然氣、以此天然氣為主成份之都市氣體、以天然氣為原料之合成液體燃料、石油系之液化石油氣、石腦油、燈油等之石油系烴類為研究對象。由此等氣體狀或液狀烴類製造氫時,一般於脫硫處理後,使烴於改質觸媒之存在下,進行部份氧化改質、自體熱改質或水蒸氣改質等之改質處理。
上述之改質處理主要取得氫與一氧化碳,而其中一氧化碳係經水與水煤氣轉化反應後可轉化為氫與二氧化碳。水煤氣轉化反應亦可使水煤氣之氫與一氧化碳之比率因應
合成反應之目的進行改變使用,亦適用於氫製造。水煤氣轉化反應所使用之銅-鋅-鋁觸媒相於貴金屬系觸媒,其可於較低溫下作用,因此可使一氧化碳濃度降至1%以下之低濃度,惟於熱及水蒸氣之存在下會產生銅之熱壓結,出現鈍化現象。故,一定條件下雖可於運轉之工業裝置下長期使用,而燃料電池類之頻繁起動、停止,使觸媒重覆於氧化,還原之氛圍時,卻容易引起銅的熱壓結、導致觸媒鈍化。使鉑等貴金屬擔載於二氧化鈦、二氧化鈰之觸媒,其耐久性雖高,低溫下之活性卻無法達銅-鋅-鋁觸媒。
因此,為改良銅-鋅-鋁觸媒之活性及耐久性,被進行各種討論,作成如下報告。
預先將氧化鋁或氧化鋁的前驅物導入反應系,以該氧化鋁或氧化鋁之前驅物為核,所形成之銅及鋅之沉澱的觸媒具良好的活性及耐久性(專利文獻1)。氧化銅、氧化鋅及氧化鋁之外,以特定量之氧化鋯與氧化錳為必須成份之觸媒其活性極高(專利文獻2)。由含有水滑石之形態的鋁及異於水滑石之鋁之兩者的觸媒前驅物所製造之觸媒極高(專利文獻3)。擔載銅於鋅鋁複合氧化物載體之觸媒於高溫下即使曝露於氧氣仍可維持高活性(專利文獻4)。
雖揭示有關如上述之改良方法,惟用於頻繁起動、停止之燃料電池時,尚無法達成足以滿意的耐久性之水準。
專利文獻1:特開2003-236382號公報
專利文獻2:特開2004-122063號公報
專利文獻3:特表2005-520689號公報
專利文獻4:特開2003-275590號公報
本發明之課題係提供一種適用於頻繁起動、停止之燃料電池仍極少降低活性,可長期使用之一氧化碳轉化用觸媒。本發明進一步之其他課題或技術之特徵更由以下記載更明瞭。
本發明者為解決該課題,進行精密研討之結果發現,針對銅-鋅-鋁觸媒,藉由下述組成及製造方法所製造之觸媒均具有良好的活性及耐久性。
亦即,本發明之一氧化碳轉化用觸媒其氧化銅成份為10~90質量%、氧化鋅成份為5~50質量%、及鋁成份為10~50質量%、比表面積為100~300m2
/g、一氧化碳吸附量為20~80μmol/g,氧化銅結晶徑為200以下。
本發明之一氧化碳轉化用觸媒係使混合含有銅鹽、鋅鹽及鋁鹽之溶液與含有氫氧化鋁之溶液所形成之沉澱物進行洗淨、乾燥及燒成後取得。
本發明之一氧化碳改性方法中使用該觸媒,於150~300℃下,經由水煤氣轉化反應後降低含有一氧化碳之含氫氣體中之一氧化碳濃度。
本發明之燃料電池系統係使用利用該一氧化碳改性方法所得之氫。
本發明之方法係以氫氧化鈉為沉澱劑,製造具有特定pH所沉澱之特定組成之銅-鋅-鋁觸媒之方法。本發明之
觸媒具有良好的活性與耐久性,搭載於作為一氧化碳轉化用觸媒之燃料電池用改質器後,即使重覆起動、停止,使用仍可減少活性的下降、長期使用之。
本發明銅-鋅-鋁系之一氧化碳轉化用觸媒之觸媒組成其氧化銅為10~90質量%,較佳者為30~80質量%,氧化鋅為5~50質量%,較佳者為5~40質量%,氧化鋁成份為10~50質量%,較佳者為15~40質量%。相較於先行技術認為最佳之觸媒,其特徵之一為氧化鋅成份少,氧化鋁成份多。
作為該觸媒組成者,當氧化銅成份不在10-90質量%時,將減少活性種之銅原子,而降低觸媒活性,相對減少鋅原子、鋁原子,導致恐將降低觸媒之耐久性(特別是重覆進行起動,停止使用狀態下,可維持滿足觸媒實用上之活性的時間。以下亦稱耐久性)。
作為該觸媒組成者,若氧化鋅成份不在5~50質量%範圍內時,則恐因減少鋅原子,而降低觸媒之耐久性,相對減少銅原子致降低觸媒活性。
作為該觸媒組成者,若氧化鋁不在10~50質量%範圍內時,則恐降低觸媒強度,降低觸媒之耐久性。又,相對減少銅原子,降低觸媒活性。
更佳者,於作為觸媒組成之氧化鋅成份中未含紅鋅礦
(zincite)。因未含紅鋅礦(zincite)可更提昇本發明之一氧化碳轉化用觸媒之耐久性、活性、搭載於作為一氧化碳轉化用觸媒之燃料電池用改質器後,有利於重覆起動停止使用仍可減少降低活性,長期使用。
本發明銅-鋅-鋁系之一氧化碳轉化用觸媒之物性其比表面積為100~300m2
/g,較佳者為120~200m2
/g、一氧化碳吸附量為20~80μmol/g,較佳者為30~70μmol/g,氧化銅結晶徑為200以下,較佳者為150以下。
氧化鋅成份至少作為鋅鋁尖晶石(ZnAl2
O4
)存在者宜。鋅鋁尖晶石愈為微細結晶者抑制銅之熱壓結之效果愈佳,結晶徑為100以下者宜,特別佳者為50以下。
紅鋅礦(zincite)、鋅鋁尖晶石之存在可藉由粉末X線繞射測定之繞射圖案確定之。
紅鋅礦(zincite)之X線繞射圖案於
d=2.475、d=2.814、d=2.602、d=1.625、d=1.477、d=1.378顯示繞射線。
鋅鋁尖晶石(ZnAl2
O4
)之X線繞射圖案於
d=2.442、d=2.863、d=1.432、d=1.559、d=1.653、d=1.281顯示繞射線。
鋅鋁尖晶石於銅原子附近則於熱及水蒸氣之存在下,具有抑制觸媒氧化、還原之氛圍重覆進行狀態之氧化銅或還原銅熱壓結後鈍化之效果,熱及水蒸氣之存在下、氧化、還原氛圍重覆進行之條件下仍穩定存在,銅之熱壓結被抑制,顯示穩定之觸媒活性。另外,氧化鋅成份為紅鋅
礦(zincite)則重覆上述氧化還原後,其紅鋅礦(zincite)粒子自體熱壓結,證明促進銅的熱壓結。
比表面積不在100~300m2
/g之範圍時,將降低觸媒活性,降低抑制銅熱壓結之效果。
一氧化碳吸附量與反應中有效銅之活性點之量有關,惟由其活性、耐久性之觀點視之,以20~80μmol/g之範圍者宜。太高則將降低耐久性。
氧化銅結晶徑若超出200則,減少反應中有效銅之活性點數,而降低活性。
鋅鋁尖晶石之結晶徑若超出100則銅之熱壓結抑制效果將下降,由耐久性面觀之為不現想者。
本發明之銅-鋅-鋁系之一氧化碳轉化用觸媒,其銅/鋅之原子比為1.0以上,及對於鋅之鋁的原子比(Zn/Al)為0.1~1.5者宜。特別理想者其銅/鋅之原子比為2~10及對於鋅之鋁的原子比(Zn/Al)為0.2~1.0。
當銅/鋅之原子比未達1.0時,則活性不足。
對於鋅之鋁的原子比(Zn/Al)不在0.1~1.5之範圍時,則燒成後鋅鋁尖晶石不會產生,或經由無充足量之產生而降低觸媒之耐久性(特別是重覆起動、停止使用狀態下,可維持滿足觸媒實用上活性之時間)、鋅原子太多產生紅鋅礦(zincite)等,其結果恐無法提昇所期待之觸媒耐久性。
本發明之銅-鋅-鋁-氧化碳轉化用觸媒係使用含有銅鹽、鋅鹽及鋁鹽之溶液與含有氫氧化鈉之溶液作成
pH7~11.5混合形成之沉澱物進行洗淨、乾燥及燒成後取得。
本發明之一氧化碳轉化用觸媒之調製係混合含有銅鹽、鋅鹽及鋁鹽之溶液與含有氫氧化鈉之溶液,使銅、鋅及鋁共沉時,攪拌任意一方,同時混合另一方亦可。此時,混合結束後的混合物pH為7~11.5,較佳者為8.5~11.0下進行之。
又,本發明一氧化碳轉化用觸媒之調製係將含有銅鹽、鋅鹽及鋁鹽溶液與含有氫氧化鈉之溶液的混合,亦可將各自之溶液以泵等同時供應混合。此時,維持混合物之pH為7~11.5,較佳者為8.5~11.0之範圍下進行。混合物之pH於7~11.5之範圍下,可取得具有充分活性與耐久性之觸媒。
混合溶液時,進行攪拌,同時使溫度維持於約0℃~約90℃,較佳者為約10℃~約80℃。
如上述,本發明之一氧化碳轉化用觸媒係使用作為沉澱劑之氫氧化鈉。先行技術中,多半以碳數鈉作為沉澱劑者宜。先行技術中,認為最適組成之高ZnO、低Al2
O3
組成範圍中,確實使用碳酸鈉之觸媒具良好的活性,惟,低ZnO、高Al2
O3
組成範圍中,使用碳酸鈉所製造之觸媒其性能卻不佳,低ZnO、高Al2
O3
組成範圍中,經由使用沉劑之氫氧化鈉後,產生微細結晶之氧化鋁尖晶石,顯示取得良好活性與耐久性之觸媒,進而完成本發明。
本發明中,作為銅及鋅之鹽類者可使用硝酸鹽、氯化
物、硫酸鹽、乙酸鹽、檸檬酸鹽等,其中又以硝酸鹽為較佳。鋁鹽可使用硝酸鹽、氯化物、硫酸鹽、氫氧化物、鋁酸鈉、擬勃姆石等,又以硝酸鹽、鋁酸鹽較佳。
本發明中,於沉澱形成後,亦可立刻洗淨、過濾、熟化後再行洗淨、過濾亦可。
本發明之乾燥條件並未特別限定,一般於室溫~200℃下之溫度進行至乾燥即可。另外,燒成條件並未特別限定,一般於150~500℃下進行燒成即可。
本發明之一氧化碳改性方法中,使用該觸媒,於150~300℃下經由水煤氣轉化反應後,降低含有一氧化碳之含氫氣中的一氧化碳濃度。
本發明燃料電池系統係使用改質碳化氫燃料後取得之氫,更使含該改質生成物中之一氧化碳濃度經由該一氧化碳改性方法下降之同時轉化成氫者為其特徵。作為本發明之燃料電池系統之原料烴燃料者,亦可任意使用LPG,都市氣體、天然氣、石腦油、燈油及輕油。
以下,藉由添附圖面,進行本發明系統更詳細之說明。圖1代表本發明系統之一實施形態之概要圖。
圖1中,容器內之氫製造用烴燃料1,首先,使脫硫器2中之含有硫化合物被脫硫處理。接著,該燃料導入改質器4進行改質處理製造氫。亦可於脫硫器2與改質器4之間,設置硫檢出器3。由改質器4取得之燃料,進一步導入填充本發明觸媒之改性器5,降低一氧化碳濃度後,導入燃料電池排氣管6,用於發電。
硫檢出器只要可測定微量之硫濃度,任意方式之測定器均可,一般代表性之方法如:紫外線螢光法(JIS K 2541-6)、乙酸鉛紙試驗法、電量滴定法等例。此等均具有可檢出、測定0.2質量ppm極微量之硫之極高精密度,為理想採用者。
本發明燃料電池用氫製造系統中所使用之脫硫器可適用任意先行技術所使用者。又,作為脫硫器所使用之脫硫劑者,並未特別限定,一般如作為先行技術之脫硫劑之公知者或慣用者,如:活性碳、沸石、或金屬系吸附劑等均適用。該脫硫劑可單獨使用,亦可組合2種以上使用之。另外,作為脫硫條件者,一般溫度選擇0~300℃之範圍,氣體之空間速度(GHSV)為200~60,000h-1
,較佳者為200~4,000h-1
之範圍,又,液體之空間速度為0.1~10 h-1
,較佳者選擇0.1~1.0 h-1
之範圍。
又,作為改質器者,可任意使用如:部份氧化改質器自體熱改質器及水蒸氣改質器等,各自適用部份氧化改質器,自體熱改質器及水蒸氣改質器之觸媒進行氫化。該改質處理中,被脫硫處理之烴燃料中硫化合物之濃度由其各改質觸媒之壽命觀之,特別以0.05質量ppm以下為宜,更佳者為0.01質量ppm以下。該部份氧化改質係藉由烴之部份氧化反應,進行氫之製造方法,部份氧化改質觸媒之存在下,一般於反應壓力常壓~5MPa、反應溫度400~1,100℃、GHSV1,000~100,000 h-1
,氧(O2
)/碳比0.2~0.8之條件下,進行改質反應。又,自體熱改質係組
合部份氧化改質與水蒸氣改質之方法,自體熱改質觸媒之存在下,一般反應壓力常壓~5MPa,反應溫度400~1,100℃,氧(O2
)/碳比0.1~1、水蒸氣/碳比0.1~10、GHSV1,000~100,000 h-1
之條件下,進行改質反應。水蒸氣改質係於烴接觸水蒸氣,製造氫之方法,水蒸氣改質觸媒之存在下,通常反應壓力常壓~3MPa、反應溫度200~900℃、水蒸氣/碳比1.5~10、GHSV1,000~100,000h-1
之條件下,進行改質反應。
本發明中,作為該部份氧化改質觸媒,自體熱改質觸媒、水蒸氣改質觸媒者,可選擇適當之先行技術公知之各觸媒使用之,其中又特別以釕系及鎳系觸媒較為理想使用者。又,作為此等觸媒之載體者,如:氧化錳、氧化鈰、及氧化鋯之例。此等載體可單獨使用1種,亦可組合2種以上使用之,或由金屬氧化物所成之載體亦可,另外,亦可於氧化鋁等其他耐火性多孔質無機氧化物中含有該金屬氧化物所成之載體。
本發明之系統,亦包含具有改質器與以藉由該改質器所製造之氫氣作為燃料之燃料電池的燃料電池系統,經由脫硫器所脫硫之燃料係由水箱混合經由水泵之水,接著送入與由空氣排氣管所送出之空氣混合之改質器。改質器中填入該改質觸媒,由送入改質器之烴燃料(如:含有源於液化石油之氣體與水蒸氣及氧之混合氣體)經由任意之上述改質反應,進行氫的製造。
如此所製造之氫氣,導入填充本發明觸媒之CO改性
器,CO濃度降至不影響燃料電池特性之程度。必要時,於導入燃料電池之前,更可設置CO選擇氧化器。作為該CO選擇氧化觸媒者,如:釕系觸媒、鉑系觸媒、或此等混合觸媒等例。
本發明燃料電池系統中,於負極側連接改質器之燃燒器後,殘留氫可作為燃料使用。又,於正極側連接氣水分離器,供應於正極側之空氣中之氧與氫之結合所產生之水與廢氣進行分離後,水可適用於水蒸氣之生成。燃料電池中伴隨發電,產生熱,因此附設排熱回收裝置後,將該熱回收之後,可有效利用。排熱回收裝置係具備捕集附設於燃料電池之反應時所生成之熱的熱交換器與為使於該熱交換器所捕集之熱與水進行熱交換之熱交換器、及冷卻器、以及此等熱交換器與往冷卻器循環冷媒之泵,於熱交換器取得之溫水可有效適用於其他設備等。
[實施例1]
將94.4g之硝酸銅三水合物,37.4g之硝酸鋅六水合物及110.0g之硝酸鋁九水合物,溶於1L之水中,作為A液。進行調合氫氧化鈉2N溶液。將A液與氫氧化鈉溶液同時滴入裝有55℃之300ml水之容器中。滴入時,攪拌沉澱物,同時維持於55℃,調整pH為9.0~9.5之氫氧化鈉溶液之滴入速度。過濾該沉澱物,充分進行水洗。將取出之沉澱物於120℃下進行乾燥後,350℃下進行燒成3
小時,作成觸媒。該觸媒組成為氧化銅55.3質量%,氧化鋅19.2質量%,及氧化鋁25.4質量%。將觸媒進行壓縮成型及粉碎,整粒為0.5~1mm。
[實施例2]
將沉澱物維持於pH11~11.5之外,與實施例1同法調製。該觸媒組成為氧化銅62.9質量%,氧化鋅21.3質量%及氧化鋁15.7質量%。
[實施例3]
將沉澱物維持於pH10~10.5之外,與實施例1同法調製。該觸媒組成為氧化銅58.8質量%,氧化鋅21.0質量%及氧化鋁20.2質量%。
[實施例4]
使用95.1g之硝酸銅三水合物,54.8g之硝酸鋅六水合物,及73.6g之硝酸鋁九水合物,將沉澱物之pH維持於10~10.5之外,與實施例1同法調製。該觸媒組成為氧化銅56.1質量%,氧化鋅29.1質量%,及氧化鋁15.0質量%。
[實施例5]
使用95.1g之硝酸銅三水合物,18.3g之硝酸鋅六水合物及147.2g之硝酸鋁九水合物,將沉澱物pH維持於
8.5~9.0除外,與實施例1同法調製。該觸媒之組成為氧化銅55.7質量%,氧化鋅10.4質量%,及氧化鋁33.9質量%。
[實施例6]
使用133.1g之硝酸銅三水合物,21.9g之硝酸鋅六水合物,及66.2g之硝酸鋁九水合物,使沉澱物pH維持於9.5~10.0之外,與實施例1同法調製。該觸媒之組成為氧化銅75.5質量%、氧化鋅11.6質量%、及氧化鋁12.9質量%。
[實施例7]
使用84.5g之硝酸銅三水合物,48.7g之硝酸鋅六水合物,及106.3g之硝酸鋁九水合物之外,與實施例1同法調製。該觸媒之組成為氧化銅49.7質量%,氧化鋅25.5質量%,及氧化鋁24.8質量%。
[實施例8]
使用57.0g之硝酸銅三水合物,51.2g之硝酸鋅六水合物,及154.5g之硝酸鋁九水合物之外,與實施例1同法調製。該觸媒之組成為氧化銅35.0質量%,氧化鋅27.2質量%,及氧化鋁37.8質量%。
[比較例1]
將市售之銅-鋅-鋁觸媒(zudochemi觸媒公司製MDC-7)進行粉碎,整粒成0.5~1mm使用之。組成為氧化銅41.3質量%,氧化鋅49.0質量%、及氧化鋁9.7質量%。
[比較例2]
使用69.2g之硝酸銅三水合物,96.3g之硝酸鋅六水合物,及40.1g之硝酸鋁九水合物,使沉澱物pH維持於7.5~8.0之外,與實施例1同法調製。該觸媒之組成為氧化銅42.0質量%,氧化鋅48.1質量%,及氧化鋁9.9質量%。
[比較例3]
使用69.2g之硝酸銅三水合物,96.3g之硝酸鋅六水合物,及40.1g之硝酸鋁九水合物,使用碳酸鈉2N溶液取代氫氧化鈉,將沉澱物pH維持於8.5~9.0之外,與實施例1同法調製。該觸媒之組成為氧化銅41.0質量%,氧化鋅49.3質量%,及氧化鋁9.5質量%。
[比較例4]
使沉澱物pH維持於6.5~7.5之外,與比較例3同法調製。該觸媒組成為氧化銅41.4質量%,氧化鋅48.9質量%及氧化鋁9.7質量%。
[實施例5]
使用碳酸鈉2N溶液取代氫氧化鈉,將沉澱物pH維持於6.0~7.0之外,與實施例1同法調製。該觸媒組成為氧化銅56.6質量%,氧化鋅16.4質量%,及氧化鋁26.9質量%。
[比較例6]
使用95.1g之硝酸銅三水合物,73.1g之硝酸鋅六水合物及36.8g之硝酸鋁九水合物之外,使沉澱物pH維持於10.5~11.0之外,與實施例1同法調製。該觸媒之組成為氧化銅58.6質量%,氧化鋅38.5質量%,及氧化鋁2.9質量%。
[比較例7]
使用95.1g之硝酸銅三水合物,及91.4g之硝酸鋅六水合物,使沉澱物pH維持於10.5~11.0之外,與實施例1同法調製。該觸媒之組成為氧化銅54.7質量%,氧化鋅45.3質量%,及氧化鋁0.0質量%。
[比較例8]
使用95.1g之硝酸銅三水合物,184.0g之硝酸鋁九水合物,使沉澱物pH維持於6.0~7.0之外,與實施例1同法調製。該觸媒之組成為氧化銅54.5質量%,氧化鋅0.0質量%及氧化鋁45.5質量%。
[觸媒之物性測定]
(a)表面積測定
表面積測定係利用湯淺離子公司製比表面積測定裝置,將100mg試料填入試料管中,作為前處理者於200℃下20分鐘之氮氣流中進行加熱脫水。接著,吸附於液體氮溫度下流通氮(30%)/氦(70%)混合氣體之氮,由脫離TCD檢出器所測定氮之吸附量求出比表面積。
(b)CO吸附量測定
CO吸附量測定係使用波動吸附量測定裝置R6015(大倉理研製),依波動法進行測定之。秤取200mg試料,作為前處理者於100%-氫,進行200℃,60分鐘還原處理。之後,於200℃、60分鐘He下進行精煉。測定方式係於50℃下,將CO氣體以波動導入。重覆進行CO波動,至未出現CO之吸附為止,測定CO之吸附量。
(c)XRD測定
XRD測定係利用理學公司製X線繞射裝置進行。將試料填入玻璃製試料吸收池,藉由X線源Cu-K α(1.5406,石墨單色計之單色化),2 θ-θ反射法進行測定。由歇勒式算出CuO、ZnAl2
O4
之結晶徑。(有關ZnAl2
O4
之結晶徑係針對實施例1、6、8及比較例1進行測得)。
(d)組成份析
觸媒之Cu、Zn、Al量係依電漿發光(ICP)法所定量。由Cu、Zn、Al之定量值求出CuO、ZnO、Al2
O3
量,使合計換算為100質量%。
[觸媒之活性評定方法]
將整粒成0.5~1mm之各0.5cc觸媒中加入4mL之SiC者填入內徑12mm之反應管中。反應管內,使觸媒於H2
/N2
=20/80之氣流中,230℃下進行2小時之還原處理後,於GHSV:60,000h-1
之條件下導入H2
/CO/CO2
/H2
O=49.9/9.9/10.2/30.0(vol%)之氣體後,於200℃下進行一氧化碳改性反應。將取得氣體進行採樣,以氣體層析法測定其濃度。此結果,同時藉由下式求出CO轉化率。其結果示於表1。
CO轉化率(%)=((A-B)/A)×100
上式中,A=反應器入口側之CO量=(改性前之CO濃度(vol%))×(改性前之氣體量(mL/分鐘))及B=反應器出口側之CO量=(改性後之CO濃度(vol%))×(改性後之氣體量(mL/分鐘))。
該觸媒之物性測定及觸媒之活性評定方法之結果記於表1及表2。
[表1]
[觸媒之耐久性評定]
將整粒成0.5~1mm之3mL觸媒填入內徑16mm之石英反應管。反應管內,使觸媒於H2
/N2
=20/80%之氣流中,230℃下進行2小時之還原處理後,於GHSV:2,500h-1
之條件下,導入H2
/CO/CO2
/H2
O=49.9/9.9/10.2/30.0(vol%)之氣體,200℃下進行1小時CO改性反應,於水蒸氣下進行精煉,同時冷卻至50℃。停止水蒸氣維持1小時。於200℃、1小時反應、與50℃之冷卻重覆進行之。經由重覆進行之活性降低傾向評定其耐久性。以實施例1之觸媒與比較例1之觸媒進行之。表3顯示藉由重覆次數之CO轉化率之下降。
<in-situ XRD之觸媒的物性變化>
利用原位XRD裝置,進行下述之A~F一連串之處理,處理後,檢測銅、鋅之化合物狀態及結晶粒徑變化。
A:乾燥處理(N2
,100℃,30分)
B:於氫之還原處理(20%H2
/80%N2
,250℃,2小時)
C:水蒸氣處理(30%H2
O/14%H2
/56%N2
,250℃,2小時)
D:降至室溫(N2
,室溫)
E:水蒸氣凝縮處理(44%H2
O/11%H2
/45%N2
,70℃,1小時)
F:於氫之再還原處理(20%H2
/80%N2
,250℃,1小時)
表4所示之實施例1、6、8之觸媒中氧化鋅成份非紅鋅礦(zincite),為ZnAl2
O4
存在之。ZnAl2
O4
即使任意進行還原處理、水蒸氣處理,水蒸氣凝縮處理之任意處理,其粒徑均不變,為極穩定者。又,氧化銅於還原處理下成銅之變化,惟粒徑即使進行上述之任意處理仍呈穩定狀態幾乎無變化。
相較於此,比較例1之觸媒中鋅係為紅鋅礦(zincite)存在,非為ZnAl2
O4
存在之。因此,觸觸中之銅無論進行還原處理、水蒸氣處理、水蒸氣凝縮處理之任意處理,其粒徑均增加。且,不僅銅、鋅亦增加其粒徑。
<XAFS之觸媒的物性變化>
藉由XAFS進行實施例1及比較例1之觸媒的解析。又,比較藉由XAFS進行紅鋅礦(zincite)及ZnAl2
O4
樣品所解析之實施例1及比較例1之解析結果示於圖2(實施例1觸媒之Zn-K XAFS解析結果)、圖3(比較例1觸媒之Zn-K XAFS解析結果)。
由圖2結果顯示,實施例之觸媒中,其波峰位置與ZnAl2
O4
相同,與紅鋅礦(zincite)不同。
由圖3結果顯示,比較例之觸媒中,其波峰位置與紅鋅礦(zincite)相同,與ZnAl2
O4
不同。
因此,可作成以下之結論。
實施例觸媒中鋅成份為ZnAl2
O4
存在之,不存在紅鋅礦(zincite)。
比較例觸媒中鋅成份為紅鋅礦存在之,不存在ZnAl2
O4
。
1‧‧‧氫製造用燃料
2‧‧‧脫硫器
3‧‧‧硫檢出器
4‧‧‧改質器
5‧‧‧改性器
6‧‧‧燃料電池排氣管
[圖1]代表本發明燃料電池用氫製造系統之一實施形態的概略圖。
[圖2]代表本發明實施例1觸媒之Zn-K XAFS解析結果。
[圖3]代表比較例1觸媒之Zn-K XAFS解析結果。
Claims (15)
- 一種一氧化碳轉化用觸媒,其係氧化銅成份為10~90質量%、氧化鋅成份為5~50質量%及氧化鋁成份為10~50質量%者,且比表面積為100~300m2 /g,一氧化碳吸附量為20~80μmol/g,氧化銅結晶粒子徑為200以下,鋅對於鋁之原子比(Zn/Al)為0.1~1.0,氧化鋅成份不含紅鋅礦(zincite)。
- 如申請專利範圍第1項之一氧化碳轉化用觸媒,其中,氧化銅成份為30~80質量%、氧化鋅成份為5~40質量%及氧化鋁成份為15~40質量%。
- 如申請專利範圍第1或2項之一氧化碳轉化用觸媒,其中,氧化鋅成份至少是來自於ZnAl2 O4 之鋅原子與氧原子。
- 如申請專利範圍第1或2項之一氧化碳轉化用觸媒,其中,銅/鋅之原子比為1.0以上。
- 如申請專利範圍第1項之一氧化碳轉化用觸媒,其中,氧化銅之結晶粒子徑為150以下。
- 如申請專利範圍第3項之一氧化碳轉化用觸媒,其中,鋅鋁尖晶石的結晶粒子徑為100以下。
- 如申請專利範圍第1項之一氧化碳轉化用觸媒,其中,比表面積為120~200m2 /g。
- 如申請專利範圍第1項之一氧化碳轉化用觸媒,其中,一氧化碳吸附量為30~70μmol/g。
- 如申請專利範圍第1項之一氧化碳轉化用觸媒,其 係混合含銅鹽、鋅鹽及鋁鹽之溶液與含氫氧化納之溶液後,使其所形成的沉澱物經過洗淨、乾燥及燒成而獲得。
- 如申請專利範圍第9項之一氧化碳轉化用觸媒,其中,含銅鹽、鋅鹽及鋁鹽之溶液與含氫氧化納之溶液的混合物,其pH值為7~11.5。
- 如申請專利範圍第9項之一氧化碳轉化用觸媒,其中,含銅鹽、鋅鹽及鋁鹽之溶液與含氫氧化納之溶液的混合物,其pH值為8.5~11.0。
- 一種一氧化碳之轉化方法,其係使用申請專利範圍第1~11項中任一項之觸媒,在150~300℃下,藉由水煤氣轉化反應(water-gas shift reaction)使含有一氧化碳之含氫氣體中的一氧化碳濃度降低。
- 一種燃料電池系統,其係使用申請專利範圍第12項之一氧化碳轉化方法用後所得的氫。
- 如申請專利範圍第13項之燃料電池系統,其係使用烴系燃料改性後所得的氫。
- 如申請專利範圍第14項之燃料電池系統,其中,烴系燃料為LPG、都市氣體、天然氣體、石腦油、燈油以及輕油之任一者。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006280188 | 2006-10-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW200836833A TW200836833A (en) | 2008-09-16 |
TWI495508B true TWI495508B (zh) | 2015-08-11 |
Family
ID=39282900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW096138276A TWI495508B (zh) | 2006-10-13 | 2007-10-12 | Carbon monoxide conversion catalyst and the use of one of the carbon dioxide modification method |
Country Status (8)
Country | Link |
---|---|
US (1) | US7776785B2 (zh) |
EP (1) | EP2067527A4 (zh) |
JP (1) | JP5666777B2 (zh) |
KR (1) | KR101455416B1 (zh) |
CN (1) | CN101522303B (zh) |
CA (1) | CA2666204C (zh) |
TW (1) | TWI495508B (zh) |
WO (1) | WO2008044707A1 (zh) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2681411C (en) * | 2007-04-10 | 2015-11-03 | Idemitsu Kosan Co., Ltd. | Catalyst precursor substance, and catalyst using the same |
CN101733109B (zh) * | 2008-11-06 | 2012-09-05 | 南化集团研究院 | 一种铜基催化剂的制备方法 |
JP5492620B2 (ja) * | 2010-03-23 | 2014-05-14 | 出光興産株式会社 | 一酸化炭素転化用触媒、その製造方法、一酸化炭素転化方法および燃料電池システム用水素の製造方法 |
JP2011194362A (ja) * | 2010-03-23 | 2011-10-06 | Idemitsu Kosan Co Ltd | 一酸化炭素転換用触媒の製造方法 |
JP5619598B2 (ja) * | 2010-12-28 | 2014-11-05 | 出光興産株式会社 | 銅−亜鉛−アルミニウム触媒、その製造方法、一酸化炭素変成方法、及び水素製造方法 |
RU2457028C1 (ru) * | 2011-06-14 | 2012-07-27 | Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" | Способ приготовления катализатора для низкотемпературной конверсии оксида углерода водяным паром |
CN104136116B (zh) * | 2011-07-27 | 2017-02-08 | 沙特阿拉伯石油公司 | 用于从气态烃中除去硫化合物的催化组合物、制造它们的方法及其用途 |
DE102012221461A1 (de) * | 2011-11-30 | 2013-06-06 | Robert Bosch Gmbh | Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems |
IN2014CN04300A (zh) * | 2011-12-12 | 2015-09-04 | 3M Innovative Properties Co | |
US8906227B2 (en) | 2012-02-02 | 2014-12-09 | Suadi Arabian Oil Company | Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds |
WO2014059513A1 (en) * | 2012-09-26 | 2014-04-24 | Enerkem, Inc. | Synthesis gas separation and reforming process |
US8920635B2 (en) | 2013-01-14 | 2014-12-30 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
JP6543971B2 (ja) * | 2014-03-11 | 2019-07-17 | 東ソー株式会社 | 芳香族ニトロ化合物用水素化触媒とその製造方法 |
WO2016145023A1 (en) * | 2015-03-10 | 2016-09-15 | Ph Matter, Llc | Chromium-free water-gas shift catalyst and process for making the same |
CN105413708B (zh) * | 2015-11-09 | 2017-12-05 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种低浓度空气污染物净化材料的制备方法 |
US10744140B2 (en) * | 2016-08-01 | 2020-08-18 | Power Supplements, Llc | Synergistic nutraceutical beverage formulations providing enhanced thermogenesis, mental clarity, and stamina while minimizing adrenaline and dopamine concentration perturbations associated with withdrawal |
KR102044877B1 (ko) * | 2016-11-09 | 2019-11-14 | 한국에너지기술연구원 | 일산화탄소 고선택성 흡착제 및 이의 제조방법 |
WO2018216555A1 (ja) * | 2017-05-25 | 2018-11-29 | 大阪瓦斯株式会社 | ガスの脱硫剤および脱硫方法 |
CN108435182B (zh) * | 2017-08-16 | 2021-01-15 | 西安向阳航天材料股份有限公司 | 一种铜系低温变换催化剂的制备方法 |
CN109745988B (zh) * | 2017-11-08 | 2022-03-01 | 中国石油天然气股份有限公司 | Cu基水煤气变换反应催化剂的制备方法 |
KR102608353B1 (ko) * | 2021-08-27 | 2023-12-01 | 울산과학기술원 | 이산화탄소 환원 촉매 복합체 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5990040A (en) * | 1995-01-11 | 1999-11-23 | United Catalysts Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation |
US20050181247A1 (en) * | 2002-05-21 | 2005-08-18 | Ceramic Fuel Cells Limited | Fuel cell system |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1296212A (zh) * | 1969-03-04 | 1972-11-15 | ||
EP0234745B1 (en) * | 1986-01-29 | 1991-06-12 | Dyson Refractories Limited | Catalysts |
CN1321136A (zh) * | 1999-09-10 | 2001-11-07 | 大金工业株式会社 | 氢气发生装置及使用该装置的燃料电池 |
JP3482459B2 (ja) | 2000-03-06 | 2003-12-22 | 独立行政法人産業技術総合研究所 | メタノールの部分酸化反応による水素製造触媒及びその製造法 |
JP2003236382A (ja) | 2002-02-14 | 2003-08-26 | Nippon Oil Corp | 水性ガスシフト反応用触媒 |
JP2003275590A (ja) | 2002-03-19 | 2003-09-30 | Toyota Central Res & Dev Lab Inc | 水性ガスシフト反応用触媒 |
US6627572B1 (en) * | 2002-03-22 | 2003-09-30 | Sud-Chemie Inc. | Water gas shift catalyst |
US6693057B1 (en) | 2002-03-22 | 2004-02-17 | Sud-Chemie Inc. | Water gas shift catalyst |
US20030191200A1 (en) * | 2002-04-08 | 2003-10-09 | Jianhua Yao | Synthesis gas conversion and novel catalysts for same |
JP4016100B2 (ja) | 2002-06-11 | 2007-12-05 | 独立行政法人産業技術総合研究所 | 水性ガスシフト反応用触媒 |
JP4336308B2 (ja) * | 2002-05-22 | 2009-09-30 | 株式会社ジャパンエナジー | 石油留分を脱硫するための吸着脱硫剤、それを用いた脱硫方法及び該脱硫方法を含む軽油の製造方法 |
JP3837520B2 (ja) | 2002-10-07 | 2006-10-25 | 独立行政法人産業技術総合研究所 | Coシフト反応用触媒 |
JP2004202310A (ja) | 2002-12-24 | 2004-07-22 | Toyota Central Res & Dev Lab Inc | 水性ガスシフト反応用触媒 |
JP2005066516A (ja) * | 2003-08-26 | 2005-03-17 | Ishikawajima Harima Heavy Ind Co Ltd | ジメチルエーテル改質触媒及びその合成方法 |
CA2681411C (en) * | 2007-04-10 | 2015-11-03 | Idemitsu Kosan Co., Ltd. | Catalyst precursor substance, and catalyst using the same |
-
2007
- 2007-10-10 KR KR1020097006342A patent/KR101455416B1/ko not_active IP Right Cessation
- 2007-10-10 US US12/445,389 patent/US7776785B2/en not_active Expired - Fee Related
- 2007-10-10 JP JP2008538742A patent/JP5666777B2/ja not_active Expired - Fee Related
- 2007-10-10 WO PCT/JP2007/069752 patent/WO2008044707A1/ja active Application Filing
- 2007-10-10 CA CA2666204A patent/CA2666204C/en not_active Expired - Fee Related
- 2007-10-10 EP EP07829490A patent/EP2067527A4/en not_active Withdrawn
- 2007-10-10 CN CN2007800376728A patent/CN101522303B/zh not_active Expired - Fee Related
- 2007-10-12 TW TW096138276A patent/TWI495508B/zh not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5990040A (en) * | 1995-01-11 | 1999-11-23 | United Catalysts Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation |
US20050181247A1 (en) * | 2002-05-21 | 2005-08-18 | Ceramic Fuel Cells Limited | Fuel cell system |
Also Published As
Publication number | Publication date |
---|---|
US20100015023A1 (en) | 2010-01-21 |
US7776785B2 (en) | 2010-08-17 |
EP2067527A4 (en) | 2013-02-06 |
KR101455416B1 (ko) | 2014-10-27 |
CA2666204C (en) | 2015-09-22 |
WO2008044707A1 (fr) | 2008-04-17 |
TW200836833A (en) | 2008-09-16 |
CN101522303B (zh) | 2013-02-06 |
CA2666204A1 (en) | 2008-04-17 |
KR20090064552A (ko) | 2009-06-19 |
JP5666777B2 (ja) | 2015-02-12 |
EP2067527A1 (en) | 2009-06-10 |
CN101522303A (zh) | 2009-09-02 |
JPWO2008044707A1 (ja) | 2010-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI495508B (zh) | Carbon monoxide conversion catalyst and the use of one of the carbon dioxide modification method | |
CA2601124C (en) | Desulfurizing agent and method of desulfurization with the same | |
JP5421770B2 (ja) | 触媒前駆体物質及びそれを用いた触媒 | |
JP4096128B2 (ja) | 脱硫剤の製造方法および炭化水素の脱硫方法 | |
WO2008001632A1 (fr) | Catalyseur pour reformage à la vapeur, appareil de production d'hydrogène, et système de pile à combustible | |
Wei et al. | Perovskite materials for highly efficient catalytic CH4 fuel reforming in solid oxide fuel cell | |
Shokrollahi Yancheshmeh et al. | Embedding Ni in Ni–Al mixed-metal alkoxide for the synthesis of efficient coking resistant Ni–CaO-based catalyst-sorbent bifunctional materials for sorption-enhanced steam reforming of glycerol | |
WO2010113506A1 (ja) | 炭化水素用脱硫剤前駆体及びその製造方法、炭化水素用脱硫剤焼成前駆体及びその製造方法、炭化水素用脱硫剤及びその製造方法、炭化水素の脱硫方法並びに燃料電池システム | |
Georgiadis et al. | Biogas dry reforming over Ni/LnOx-type catalysts (Ln= La, Ce, Sm or Pr) | |
Jahangiri et al. | Syngas production via auto-thermal methane reforming using modified perovskite catalysts: performance evaluation of La1− xGdxNiO3-δ perovskite oxides | |
Pham et al. | Syngas production from biogas reforming: role of the support in nickel-based catalyst performance | |
JP4521172B2 (ja) | 脱硫剤及びこれを用いた脱硫方法 | |
JP2005007383A (ja) | 硫黄化合物除去用吸着剤及び燃料電池用水素の製造方法 | |
Huang et al. | Insight into exhaust gas-methane reforming over La2O3-modified Ni/Ca-Al for enhanced hydrogen-rich production | |
JP2005034682A (ja) | Co変成触媒およびその製造方法 | |
Yin et al. | A Decrease in NiO‐MgO Phase Through Its Solid Solution Equilibrium with Tetragonal (La 1− z Sr z) 2 Ni 1− y Mg y O 4− δ: Effect on Catalytic Partial Oxidation of Methane | |
JP5275113B2 (ja) | 炭化水素用脱硫剤前駆体及びその製造方法、炭化水素用脱硫剤焼成前駆体及びその製造方法、炭化水素用脱硫剤及びその製造方法、炭化水素の脱硫方法並びに燃料電池システム | |
JP2010001480A (ja) | 脱硫剤及びこれを用いた脱硫方法 | |
JP2011183346A (ja) | 水素製造用触媒、その製造方法および水素製造方法 | |
JP5275114B2 (ja) | 炭化水素用脱硫剤及びその製造方法、炭化水素の脱硫方法並びに燃料電池システム | |
JP4709724B2 (ja) | 炭化水素の改質用触媒 | |
EP0599351A1 (en) | Method of desulfurization of town gas | |
JP2001276605A (ja) | 脱硫剤及び燃料電池用水素の製造方法 | |
Hou et al. | Multi-metal composite layered materials derived from ZIF-67 for enhanced toluene oxidation | |
Li et al. | Optimizing Mo-C Coordination for Enhanced Low-Temperature Water-Gas Shift Activity in Α-Moc1-X Catalysts: An Experimental and Theoretical Study |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |