WO1999046040A1 - Catalyseur pour l'extraction d'hydrocarbures de gaz d'echappement et procede de clarification de gaz d'echappement - Google Patents
Catalyseur pour l'extraction d'hydrocarbures de gaz d'echappement et procede de clarification de gaz d'echappement Download PDFInfo
- Publication number
- WO1999046040A1 WO1999046040A1 PCT/JP1999/001100 JP9901100W WO9946040A1 WO 1999046040 A1 WO1999046040 A1 WO 1999046040A1 JP 9901100 W JP9901100 W JP 9901100W WO 9946040 A1 WO9946040 A1 WO 9946040A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- exhaust gas
- zirconia
- palladium
- hydrocarbons
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 197
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 61
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000005352 clarification Methods 0.000 title 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 181
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 149
- 239000007789 gas Substances 0.000 claims abstract description 144
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 133
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 77
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- 239000010937 tungsten Substances 0.000 claims abstract description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 141
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 27
- 238000000746 purification Methods 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 11
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- XZLXGTUBUCMRCH-UHFFFAOYSA-N tungsten zinc Chemical compound [Zn].[W] XZLXGTUBUCMRCH-UHFFFAOYSA-N 0.000 claims 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 51
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 38
- 230000003197 catalytic effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 229910052815 sulfur oxide Inorganic materials 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- -1 platinum group metals Chemical class 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910052705 radium Inorganic materials 0.000 description 3
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 3
- 150000003754 zirconium Chemical class 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 101150107341 RERE gene Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- OREVZUNTMMDDSG-UHFFFAOYSA-N [W].[Zn].[Zr] Chemical class [W].[Zn].[Zr] OREVZUNTMMDDSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- OLTNQSDYEIONCS-UHFFFAOYSA-N [S].O=C=O Chemical compound [S].O=C=O OLTNQSDYEIONCS-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- XWIHRGFIPXWGEF-UHFFFAOYSA-N propafenone hydrochloride Chemical compound Cl.CCCNCC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 XWIHRGFIPXWGEF-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical class [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9431—Processes characterised by a specific device
-
- 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
- B01J23/44—Palladium
-
- 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
- B01J23/54—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
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B01J35/19—
-
- 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
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Definitions
- the present invention relates to a catalyst for purifying hydrocarbons in exhaust gas containing methane and containing excess oxygen, and a method for purifying exhaust gas.
- exhaust gas containing an excessive amount of oxygen means that the exhaust gas treated by the catalyst of the present invention has an oxygen or nitrogen amount that is at least an amount necessary for completely oxidizing the reducing component coexisting therewith. It means that the exhaust gas contains oxidizing components such as elemental oxides.
- reaction inhibitors such as sulfur oxides usually coexist in the exhaust gas, and these significantly reduce the catalytic activity with time.
- natural gas contains essentially no sulfur compounds.
- natural gas-derived city gas supplied in Japan contains sulfur-containing compounds as odorants, which generate sulfur oxides when the gas is burned. This becomes a factor inhibiting the activity of the platinum group catalyst.
- Yamamoto and colleagues also reported that in the case of oxidizing and removing hydrocarbons from city gas combustion exhaust gas using a catalyst in which platinum and palladium are supported on aluminum, it takes less than 100 hours. Reports significant reduction in catalytic activity (Preliminary proceedings of the Catalysis Society's 1996 Catalyst Research Presentations, published on September 13, 1996).
- Japanese Patent Application Laid-Open Publication No. 8-332392 discloses an oxidation catalyst for low-concentration hydrocarbons in exhaust gas in which an excessive amount of oxygen is present, via an alumina carrier on a honeycomb substrate.
- a catalyst supporting 7 g / l or more of palladium and 3 to 20 g / 1 of platinum is disclosed.
- this catalyst also does not have sufficient long-term durability, and the deterioration of the catalyst activity with time cannot be avoided.
- the conventional exhaust gas treatment technology has a low methane removal rate, and further, under conditions where sulfur oxides coexist, a sudden decrease in catalytic activity occurs within a short time. There are problems such as and.
- the exhaust gas usually contains nitrogen oxides as well as hydrocarbons.
- a method for removing nitrogen oxides and hydrocarbons in such a gas a method for removing nitrogen oxides using hydrocarbons as a reducing agent is known (for example, Japanese Patent Application Publication No. Gazette Gazette 1-310742, etc.).
- Japanese Patent Application Laid-Open No. 4-90826 discloses that a specific catalyst and an exhaust gas containing nitrogen oxides are brought into contact with each other in the presence of hydrocarbons in an oxidizing atmosphere in which an excessive amount of oxygen coexists. After decomposing, the exhaust gas comes into contact with the oxidation catalyst By controlling the emission of hydrocarbons, a method for purifying exhaust gas is disclosed.
- propane and propene are converted to carbon dioxide at a high rate under conditions where nitrogen oxides can be removed favorably.
- the percentage remaining in the gas is low.
- methane is less reactive under conditions where known nitrogen oxide removal catalysts exhibit high activity, so that large amounts of methane remain in the process gas. Inevitable. Therefore, if the exhaust gas contains methane, it is necessary to improve this point.
- Japanese Unexamined Patent Publication No. 4-90826 discloses that unreacted hydrocarbons can be removed by passing exhaust gas through a nitrogen oxide removal catalyst and then through an oxidation catalyst.
- an oxidation catalyst a catalyst having 0.01 to 2% of platinum, orifice, palladium, or the like supported on a porous carrier is mentioned. Even so, no mention is made of how this type of catalyst would react to methane. In view of the report from the above-mentioned lamps, it is hardly considered that methane in the exhaust gas can be removed by using such a catalyst.
- U.S. Pat.No. 5,260,043 discloses that a cobalt-loaded ZSM- By using a 5-catalyst followed by a palladium-supported ZSM-5 catalyst, a gas containing methane, nitrogen oxides and oxygen is treated, and nitrogen oxides and nitrogen oxides are treated. It discloses a method for purifying tungsten. However, the gas tested in the method described in this document does not contain any of steam and sulfur oxides, so there is a great doubt about the practicality of this method. You. In addition, the inventors of the patent separately disclose a description of the effect of water vapor on the methane oxidation activity of a noradium-supported ZSM-5 catalyst (Yuejin Li and John N. Armor, Considering, for example, Applied Catalysis B: Environmental, vol. 3, pp. 275 (1994)), the methane in actual exhaust gas containing water vapor can be removed by the method of the patent. It is hard to imagine.
- sulfur-containing organic compounds usually derived from proteins and the like also coexist in these exhaust gases, these sulfur-containing organic compounds are oxidized and oxidized when hydrocarbons are oxidized and removed by the catalyst. Oxides are generated, and the catalytic activity is reduced as described above.
- the present invention is directed to a catalyst for purifying hydrocarbons in an exhaust gas containing methane and containing an excessive amount of oxygen, the exhaust gas having a high proportion of methane in the total hydrocarbons.
- the catalyst in which palladium is supported on at least one carrier selected from the group shows high resistance to the inhibition of activity by sulfur oxides, and under exhaust gas conditions. High and stable It has been found that the oxidation ability is maintained.
- the inventor has proposed that when platinum is supported together with palladium on at least one kind of carrier selected from zirconia and sulfated zirconium zinc tungsten zirconia. It has been found that even at a lower treatment temperature, a high metanoxidation ability can be obtained.
- the present invention has been made based on such knowledge, and relates to the following catalyst for purifying hydrocarbon-containing exhaust gas and method for purifying hydrocarbon-containing exhaust gas.
- a catalyst for purifying hydrocarbons in an exhaust gas containing methane and containing an excess of oxygen wherein at least one kind of carrier selected from zirconia, sulfate zirconia and tungsten zirconia is used.
- a catalyst for purifying carbon dioxide in an exhaust gas containing methane and containing an excess of oxygen the catalyst being at least one selected from zirconia, sulfate zirconia and tungsten zirconia.
- the supported amount of palladium is 2 to 20% by weight relative to the carrier, and the supported amount of platinum is Item 4.
- a method for purifying hydrocarbons in exhaust gas comprising using a catalyst comprising one kind of carrier carrying palladium. 6. The loading amount of palladium is 2 to 2 by weight ratio to the carrier.
- Item 6 The method for purifying hydrocarbons in exhaust gas according to Item 5, which is 0%.
- a method for purifying hydrocarbons in exhaust gas characterized by using a catalyst in which palladium and platinum are supported on a carrier.
- Item 8 The above item 7 wherein the supported amount of palladium is 2 to 20% by weight relative to the carrier and the supported amount of platinum is 10 to 50% by weight relative to palladium.
- a method for purifying an exhaust gas containing nitrogen oxides and hydrocarbons and containing methane as a component of the hydrocarbons which is used as a catalyst for reducing nitrogen oxides in the presence of hydrocarbons.
- the exhaust gas is brought into contact with a catalyst comprising palladium supported on at least one kind of carrier selected from zirconia and sulfated zirconium zinc tungsten zirconia.
- a catalyst comprising palladium supported on at least one kind of carrier selected from zirconia and sulfated zirconium zinc tungsten zirconia.
- a method for purifying an exhaust gas containing nitrogen oxides and hydrocarbons and containing methane as a component of the hydrocarbons, wherein the nitrogen oxides are reduced in the presence of hydrocarbons After the exhaust gas is brought into contact with the catalyst, the exhaust gas is brought into contact with a catalyst comprising palladium and platinum supported on at least one carrier selected from zirconia, sulfate zirconia and tungsten zirconia. Characteristic exhaust gas purification method.
- the catalyst according to the present invention is obtained by impregnating a commercially available zirconia carrier with palladium ion or a solution containing palladium ion and platinum ion, followed by drying and calcining. And manufactured.
- the specific surface area of the zirconia support is an important factor in keeping palladium or platinum / platinum highly dispersed, and is preferably 5 m 2 / g or more. More preferably, it is in the range of 5 to 50 m 2 / g.
- As the carrier sulfate zirconia (SO 4 / ZrO 2) and titanium zirconia (WO 3 / ZrO 2 ) can also be used. Zirconia, sulfated zirconium and tungsten zirconium may be used alone or in combination of two or more.
- the sulfated zirconium carrier and the tungsten zirconia carrier can be prepared by a known method.
- sulfate sulfate zirconia is, for example, It can be obtained by treating zirconium hydroxide with dilute sulfuric acid or by impregnating zirconium hydroxide with ammonium sulfate, followed by drying and firing.
- Tungsten zirconia can be obtained, for example, by wet-kneading zirconium hydroxide and tangstenic acid, followed by drying and firing.
- the carrier is represented by a zirconium carrier.
- Solutions containing catalytic metal ions include nitrates of those metals. Solutions such as acid salts and amine complexes may be used. As the solution form, an aqueous solution is preferable, but a mixed solvent solution to which a water-soluble organic solvent such as acetone or ethanol is added may be used.
- the supported amount of palladium on the zirconia carrier is about 1 to 25%, and more preferably about 2 to 20%, based on the weight of the carrier. If the supported amount of palladium is too small, the catalytic activity will be reduced, while if it is too large, the particle size of the palladium will be large and the palladium will not be used effectively. .
- the supported amount of palladium is the same as described above, and the supported amount of platinum is usually 5 to 50% based on the weight of palladium. %, And more preferably about 10 to 50%. If the amount of supported platinum is too small, the effect of the combined use is not sufficiently improved, while if too large, the function of palladium may be impaired.
- the desired catalyst is obtained by drying the zirconia support impregnated with a predetermined amount of the catalytically active component and calcining it in air.
- the calcination is preferably in the range of about 450 to 700 ° C, more preferably in the range of about 500 to 650 ° C, in order to obtain stable and high catalytic activity over a long period of time.
- the calcination temperature is too high, the specific surface area may decrease with the progress of the grain growth of the supported metal, and the catalyst activity may decrease. As the grain growth of palladium and platinum increases, the catalytic activity decreases and the stability is impaired.
- the catalyst according to the present invention can be used in any form, such as a form in which a binder is added to form a pellet in accordance with an ordinary method, and a state in which the resin is coated on a fire-resistant honeycomb. You. It is preferable that the catalyst according to the present invention is used as a wet coat on a refractory honeycomb. In the case of wet coating on a refractory honeycomb, the catalyst prepared by the above method may be slurry-shaped and may be coated or used as a carrier. After the zirconia particles are pre-coated on the refractory honeycomb, palladium is carried on the carrier by the same method as above, and the carrier carries palladium / platinum. You may let it.
- the catalyst obtained above is used.
- the specified purification rate cannot be obtained, and the space velocity per exhaust gas hour (GHSV) is 5%.
- GHSV gas velocity per hour
- the catalyst amount used under conditions of a GHSV force 500, 000 h one 1 below, may be suitably selected.
- the catalyst for purifying hydrocarbons in methane-containing exhaust gas used in the present invention has a high activity, but if the purification treatment temperature is too low, the activity is not sufficiently exhibited, so that a desired hydrocarbon conversion is performed. It is difficult to obtain a rate. If the concentration of hydrocarbons in the exhaust gas is remarkably high, a rapid reaction occurs in the catalyst layer, which may affect the durability of the catalyst. In consideration of these points, the temperature of the catalyst layer is maintained within the range of about 350 to 600 ° C, and the temperature rise in the catalyst layer (difference between the outlet temperature and the inlet temperature of the catalyst layer) is 150 °. It is preferable to purify the exhaust gas while adjusting the reaction conditions so as to be C or less.
- a catalyst that reduces nitrogen oxides in the presence of hydrocarbons (hereinafter simply referred to as a “nitrogen oxide removal catalyst”) is provided upstream of the hydrocarbon purification catalyst.
- the catalyst for removing nitrogen oxides is not particularly limited, as long as it can reduce and remove nitrogen oxides using lower saturated hydrocarbons as a reducing agent.
- a known catalyst can be used. it can.
- Examples of such a catalyst include a transition metal ion-exchanged zeolite catalyst (for example, a catalyst in which cobalt is supported on a type zeolite carrier) and a catalyst in which silver is supported on an alumina carrier. Is mentioned.
- the amount of the nitrogen oxide removing catalyst used may be set so as to have an appropriate space velocity according to the type of the catalyst.
- the gas time This other Ri space velocity (GHSV) is 60, 000 h 1 and rather to prefer that you use in conditions that Do is, 3 0, 000 h 1 below the preferred Ri Son and of the Gayo to be used in the Do that conditions correct .
- the operating temperature is about 300 to 600 ° C, more preferably about 350 to 500 ° C.
- the operating temperatures of the nitrogen oxide removing catalyst and the hydrocarbon purifying catalyst cannot be set separately, so that the temperature is within the preferred operating temperature range of the hydrocarbon purifying catalyst and It is preferred to use both catalysts within the preferred operating temperature range of the catalyst for removing nitrogen oxides.
- nitrogen oxides are removed from exhaust gas in the presence of hydrocarbons
- the nitrogen oxide removal rate can be improved.
- the removal rate of nitrogen oxides can be improved while suppressing methane emission. That is, according to the present invention, by installing a nitrogen oxide removing catalyst in combination upstream of the hydrocarbon purifying catalyst, the nitrogen oxides are reduced, and the emission of methane is reduced. Can be suppressed.
- the exhaust gas usually contains about 5 to 15% of water vapor that inhibits the oxidation reaction of methane.
- the method of the present invention is high even for exhaust gas containing water vapor as described above. Demonstrates the methan conversion effect.
- the exhaust gas usually contains sulfur oxides, which are known to significantly reduce the catalytic activity.
- the catalyst of the present invention has a low level of activity due to sulfur poisoning. It also has a high resistance, so that the purification rate of hydrocarbons is maintained at a high level over a long period of time.
- the catalyst of the present invention exhibits a high methane oxidation activity even in the treatment of an exhaust gas containing a large amount of water vapor such as a combustion exhaust gas, and also inhibits the activity inhibition by a sulfur oxide. Even so, it has high resistance. Therefore, with conventional catalysts It maintains high purification performance over a long period of time even for exhaust gas that contains a large amount of methane as a hydrocarbon component, which was difficult.
- a catalyst for removing nitrogen oxides in the presence of hydrocarbons is disposed in the front stage, and the hydrocarbon purification catalyst of the present invention is disposed in the rear stage.
- the hydrocarbon purification catalyst of the present invention is disposed in the rear stage.
- FIG. 1 is a graph showing the change over time of the methane conversion rate in the exhaust gas when the exhaust gas treatment was performed using each of the catalyst of one example of the present invention and the catalyst of the comparative example.
- FIG. 2 is a graph showing the change over time in the methane conversion in the exhaust gas when exhaust gas treatment was performed using each of the catalysts of the other examples of the present invention and the catalyst of the comparative example.
- FIG. 3 shows the methane conversion in the exhaust gas when the exhaust gas treatment was performed using each of the catalysts of another embodiment of the present invention. This is a graph showing the change over time of the conversion rate.
- Example 1
- Example 2 5 g of the same zirconia as in Example 1 was immersed in 20 ml of an aqueous solution of palladium nitrate containing 0.25 g of palladium at 0 ° C. for 15 hours. This was dried, and further calcined in air at 550 ° C. for 2 hours to obtain a 5% Pd zirconia catalyst.
- Example 2 5 g of the same zirconium as in Example 1 was immersed in 20 ml of an aqueous solution of palladium nitrate containing 0.50 g of noradium at 0 ° C. for 15 hours. This is dried and further in air at 550 C for 2 hours Calcination gave a 10% Pd / zircoure catalyst.
- Example 2 5 g of the same zirconia as in Example 1 was immersed in 20 ml of an aqueous solution of palladium nitrate containing 1.0 g of noradium at 0 ° C. for 15 hours. This was dried and further calcined at 550 ° C. for 2 hours in air to obtain a 20% Pd zirconia catalyst.
- a solution obtained by dissolving 5 g of zirconia as in Example 1 and heating and dissolving an aqueous solution of palladium nitrate containing 0.25 g of noradium and 0.083 g of dinitrodiammineplatinum in 1 ml of 69% nitric acid The mixture was mixed with and then immersed in a 20 ml solution of pure water at 0 ° C for 15 hours. This was dried and further calcined in air at 550 ° C. for 2 hours to obtain a 5% Pd-l% Pt / zirconia catalyst.
- Example 2 5 g of the same zirconium as in Example 1 was taken, and an aqueous solution of palladium nitrate containing 0.25 g of noradium and 0.042 g of dinitrodiammineplatinum were heated and dissolved in 1 ml of 69% nitric acid. The solution was mixed with, and further immersed in a solution of 20 ml with pure water at 0 ° C for 15 hours. This is dried and further in air at 550 ° C for 2 hours. Then, 5% Pd-0.5% ⁇ 17 zirconia catalyst was obtained.
- Example 2 5 g of the same zirconia as in Example 1 was taken.
- An aqueous solution of palladium nitrate containing 0.10 g of radium and a solution prepared by heating and dissolving 0.021 g of dinitrodiammineplatinum in 1 ml of 69% nitric acid are mixed. It was immersed in a solution of 20 ml of polished at 0 ° C for 15 hours. This was dried and further calcined in air at 550 ° C. for 2 hours to obtain a 2% Pd-0.25% Pt / zirconia catalyst.
- Example 2 Take 5 g of the same zirconia as in Example 1, heat and dissolve 0.042 g of an aqueous solution of palladium nitrate containing 0.10 g of radium and 0.042 g of dinitrodiammine platinum in 1 ml of 69% nitric acid The resulting solution was mixed with, and further immersed in a 20 ml solution of pure water at 0 ° C for 15 hours. This was dried and further calcined in air at 550 ° C. for 2 hours to obtain a 2% Pd-0.5% Pt / zirconia catalyst.
- Example 1 5 g of the same zirconia as in Example 1 was taken, and an aqueous solution of palladium nitrate containing 0.10 g of noradium and 0.083 g of dinitrodiammineplatinum were heated and dissolved in 1 ml of 69% nitric acid. Mix liquid and The solution was further immersed in a 20 ml solution of pure water at 0 ° C for 15 hours. This was dried and further calcined at 550 ° C. for 2 hours in air to obtain a 2% Pd-l% Pt zirconia catalyst. Comparative Example 1
- Alumina manufactured by Sumitomo Chemical (Co.); NK-1 24 was calcined for 2 hours at 800 ° C in air. 5 g of the solution was immersed in 20 ml of an aqueous solution of palladium nitrate containing 0.25 g of noradium at 0 ° C for 15 hours. This was dried and further calcined in air at 550 ° C. for 2 hours to obtain a 5% Pd / alumina catalyst (1).
- Aluminum (Sumitomo Chemical Co., Ltd .: NK-124) was fired in air at 800 ° C for 2 hours. Take 5 g of this, and then An aqueous solution of palladium nitrate containing 0.25 g of radium and a solution of 0.085 g of dinitrodiammineplatinum dissolved in 2 ml of nitric acid are mixed and diluted. The solution was then immersed in a 20 ml solution at 0 ° C for 15 hours. This was dried and further calcined in air at 550 ° C. for 2 hours to obtain a 5% Pd-1% Pt / alumina catalyst.
- Titania (ST-21, manufactured by Ishihara Sangyo Co., Ltd.) was fired in air at 800 C for 2 hours. 5 g of this was taken and immersed in 20 ml of an aqueous solution of palladium nitrate containing 0.25 g of palladium at 0 ° C. for 15 hours. This is dried and further fired in air at 550 ° C for 2 hours.
- Each of the catalysts obtained in Examples 1 to 9 and Comparative Examples 1 to 5 was tableted and sized to a particle size of 1 to 2 mm.
- 1 ml of each compact was used as a catalyst layer, and 1000 ppm of methane, 10% of oxygen, 6% carbon dioxide, 10% water vapor, is circulated by sulfur dioxide 8 ppm, GHSV re ⁇ Mukaka et na Ru composition of the gas to the remainder (gas hourly those other Ri spatial velocity) 40, 000h 1 conditions, the catalyst
- the change in methane conversion over time was measured while maintaining the bed temperature at about 500 ° C.
- the gas composition before and after the reaction layer was measured by gas chromatography with a hydrogen flame ionization detector.
- the methane conversion before adding 8 ppm of sulfur dioxide to the reaction gas was also measured in advance.
- Table 1 shows the methane conversion (%) at 3, 10, 18, 19 and 22 hours after the start of the distribution of the sulfur dioxide-containing gas.
- the methane conversion is a value obtained by the following equation.
- CH 4 conversion rate (%) 100X (1-catalyst layer outlet CH 4 / catalyst layer inlet CH 4 )
- Each of the catalysts obtained in Examples 2, 6 and 9 and Comparative Examples 1 and 4 was tableted and sized to a particle size of 1 to 2 mm.
- a gas consisting of 1000 ppm of methane, 10% of oxygen, 6% of carbon dioxide, 10% of water vapor, 8 ppm of sulfur dioxide, and the balance of helium was replaced with GHSV (0.75 ml of each catalyst layer).
- the gas composition before and after the reaction layer was measured by gas chromatography with a hydrogen flame ionization detector. Table 2 shows the change over time in the methane conversion (%).
- the value for the second hour is the value at a gas hourly space velocity (GHSV) of 4,000h- 1 .
- GHSV gas hourly space velocity
- Example 2 and Comparative Example 1 Each of the catalysts obtained in Example 2 and Comparative Example 1 was tableted and sized to a particle size of 1 to 2 mm. Next, 1.5 ml of each was used as a catalyst layer, and 2,000 ppm of methane, 1 OOOppm of carbon monoxide, 10% of oxygen, 6% of carbon dioxide, 10% of steam, 0.3% of sulfur dioxide, and 0.3 ppm of residual nitrogen were used as catalyst layers.
- the Do that composition of gas GHSV was circulated at (gas hourly those other Ri space velocity) 80, the 000 h 1 conditions, the catalyst layer temperature kept at about 450 ° C, it was subjected to a durability evaluation test of the catalyst.
- the gas composition before and after the reaction layer was determined by gas chromatography with a hydrogen flame ionization detector.
- Figure 1 shows the change over time in the methane conversion (%).
- the catalyst of Comparative Example 1 exhibited a methane conversion activity equal to or higher than that of the catalyst of Example 2 immediately after the start of the test, but showed sulfur dioxide. Due to the presence of the compound, it rapidly degrades and loses its activity substantially within a short time. On the other hand, the catalyst of Example 2 showed a stable long-term conversion of methane even in the presence of sulfur dioxide. Continue to maintain activity.
- the catalyst of Example 5 was tableted, sized to a particle size of 1 to 2 mm, and 0.75 ml of the catalyst was used as a catalyst layer. 1000 ppm of methane, 10% of oxygen, 6% of carbon dioxide, 10% of water vapor, and 10% of carbon dioxide sulfur 2.7ppm the remainder f Li ⁇ Mukaka et GHSV gas name Ru composition (gas hourly those other Ri empty i3 ⁇ 4 rate) 40, 000h one 1 I trowel 2 U temple, 80 in the next Rere, 000h one 1 of Article The test was conducted to evaluate the conversion of methane (durability as a catalyst) while maintaining the catalyst layer temperature at about 450 ° C. The gas composition before and after the reaction layer was measured by gas chromatography with a hydrogen flame ionization detector. Table 3 shows the change over time of the methane conversion (%).
- Example 5 Except that the catalyst of Example 5 was tableted and sized to a particle size of 1 to 2 mm, 0.75 ml of which was used as the catalyst layer, and the temperature of the catalyst layer was 400 ° C, the same as Example 11 A durability evaluation test of the catalyst was performed under the same conditions. Table 4 shows the change over time in the methane conversion (%).
- the values at the 1st and 2nd hour are the values at the gas hourly space velocity (GHSV) 40,000 h- 1 .
- Ngusute phosphate (H 2 WO 4, manufactured by Mitsuwa Chemicals Co.) 15 was added to the g and water 140 g, 7 h at room temperature And stirred. This was dried at 120 ° C for 2 hours and baked at 700 ° C for 6 hours to obtain tungsten stainless steel.
- the product had a specific surface area of 76 m 2 / g as determined by the BET method, and the X-ray diffraction showed a mainly tetragonal pattern.
- Example 15 10 g of tungsten zirconia prepared in the same manner as in Example 15 was used, and an aqueous solution of palladium nitrate containing 0.5 g of noradium and an aqueous solution of palladium nitrate containing 0.1 g of platinum were taken.
- the solution was mixed and stirred with an aqueous solution of minium platinum nitrate, pure water was added thereto, and the mixture was immersed in a solution having a volume of 7 ml to impregnate palladium and platinum. Then, it is dried and further calcined in air at 550 ° C for 9 hours to obtain 5% Pd-1% Pt / tungsten zirconium. I got it.
- Each of the catalysts obtained in Examples 15 and 16 was tableted and sized to a particle size of 1 to 2 mm. Next, a gas consisting of 1000 ppm of methane, 10% of oxygen, 6% of carbon dioxide, 10% of water vapor, 8 ppm of sulfur dioxide, and 8 ppm of residual helium was used as a catalyst layer with 0.75 ml of each as a catalyst layer.
- Table 5 shows the change with time of (%).
- the values at the 1st and 2nd hour are the values at a gas hourly space velocity (GHSV) of 40,000h- 1 .
- GHSV gas hourly space velocity
- Example 17 and Comparative Example 1 were each tablet-molded and sized to a particle size of 1 to 2 mm.
- a gas consisting of 1000 ppm of methane, 10% of oxygen, 6% of carbon dioxide, 9% of steam, 3 ppm of sulfur dioxide, and 3 ppm of helium as the catalyst layer was used as a catalyst layer with 1.5 m1 of each gas as GHSV. is circulated at (space velocity Ri per gas hourly) 80, 0 00h 1, the catalyst layer temperature kept at about 450 Q C, were catalyst evaluation test.
- the gas composition before and after the reaction layer was measured by gas chromatography with a hydrogen flame ionization detector.
- Figure 2 shows the change over time in the methane conversion (% :).
- the catalyst of Example 16 was tableted and sized to a particle size of 1 to 2 mm. In the next stage, 1.5 ml of the mixture was taken and 2,000 ppm of methane was used.
- GHSV gas composed of lOOOO ppm of carbon oxide, 10% of oxygen, 6% of carbon dioxide, 10% of steam, 0.3 ppm of sulfur dioxide, and the balance of nitrogen
- Space velocity per gas hour 80,000h 1 Flowed under the conditions of 1 and the catalyst layer temperature was maintained at approx. Test was carried out.
- the gas composition before and after the reaction layer was measured by a gas chromatograph equipped with a hydrogen flame ionization detector.
- Figure 3 shows the change over time in the methane conversion (%).
- the catalyst according to Example 16 of the present invention shows stable catalytic activity even in the presence of sulfur dioxide, which rapidly reduces the catalytic activity.
- Example 22 Cobalt ion exchange similar to that of Example 21) 6 ml of 3-zeolite catalyst was placed upstream in the reaction tube, and 1 ml of 5% Pd zirconia catalyst was placed downstream, and the reaction was carried out. With the temperature of the tube maintained at about 450 ° C, 100 ppm of nitric oxide, 1600 ppm of methane, 110 ppm of ethane, 70 ppm of pronon, 35 ppm of n-butane, 10% of oxygen, 9% of steam, 9% of CO2 A gas consisting of 0.3 ppm of sulfur and the balance of nitrogen was passed at a flow rate of 1 liter per minute (converted to 0 ° C), and the conversion and remaining nitrogen oxides (NOx) after the start of the reaction. The methane concentration was measured. Table 7 shows the results.
- Example 2 6 ml of cobalt ion exchange / 3-zeolite catalyst similar to 1 was placed on the upstream side of the reaction tube, and 1 ml of 5% Pd / Alumina catalyst (1) was placed on the downstream side. While maintaining the temperature of the reaction tube at about 450 ° C, 100 ppm of nitric oxide, 1600 ppm of methane, 110 ppm of ethane, 70 ppm of propane, 35 ppm of n-butane, and 1 ppm of oxygen Gas with a composition consisting of 0%, steam 9%, sulfur dioxide 0.3ppm, and the balance of nitrogen is passed at a flow rate of 1 liter per minute (0 ° C conversion), and nitrogen oxidation after the start of the reaction. The conversion of the product (NOx) and the residual methane concentration were measured. Table 8 shows the results.
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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DK99939143T DK1063010T3 (da) | 1998-03-09 | 1999-03-08 | Fremgangsmåde til fjernelse af methan fra udstödningsgasser |
US09/622,469 US6602481B1 (en) | 1998-03-09 | 1999-03-08 | Catalyst for removing hydrocarbons from exhaust gas and method for clarification of exhaust gas |
DE69939011T DE69939011D1 (de) | 1998-03-09 | 1999-03-08 | Verfahren zur entfernung von methan aus abgasen |
EP99939143A EP1063010B1 (en) | 1998-03-09 | 1999-03-08 | Method for removing methane from exhaust gas |
US10/459,963 US6887446B2 (en) | 1998-03-09 | 2003-06-12 | Catalyst for removing hydrocarbons from exhaust gas and method for purification of exhaust gas |
US10/838,552 US7371706B2 (en) | 1998-03-09 | 2004-05-04 | Catalyst for removing hydrocarbons from exhaust gas and method for purification of exhaust gas |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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JP10/56867 | 1998-03-09 | ||
JP5686798 | 1998-03-09 | ||
JP35442298A JP4304385B2 (ja) | 1998-12-14 | 1998-12-14 | 排ガス中のメタンの酸化除去用触媒および排ガス中のメタンの酸化除去方法 |
JP10/354422 | 1998-12-14 | ||
JP11017410A JP2000210535A (ja) | 1999-01-26 | 1999-01-26 | 天然ガス燃焼排ガスの浄化方法および天然ガス燃焼排ガスの浄化装置 |
JP11/17415 | 1999-01-26 | ||
JP11/17410 | 1999-01-26 | ||
JP11017415A JP2000210536A (ja) | 1999-01-26 | 1999-01-26 | 燃焼排ガスの浄化方法および燃焼排ガスの浄化装置 |
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US09622469 A-371-Of-International | 1999-03-08 | ||
US09/622,469 A-371-Of-International US6602481B1 (en) | 1998-03-09 | 1999-03-08 | Catalyst for removing hydrocarbons from exhaust gas and method for clarification of exhaust gas |
US10/459,963 Continuation US6887446B2 (en) | 1998-03-09 | 2003-06-12 | Catalyst for removing hydrocarbons from exhaust gas and method for purification of exhaust gas |
US10/838,552 Division US7371706B2 (en) | 1998-03-09 | 2004-05-04 | Catalyst for removing hydrocarbons from exhaust gas and method for purification of exhaust gas |
Publications (1)
Publication Number | Publication Date |
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WO1999046040A1 true WO1999046040A1 (fr) | 1999-09-16 |
Family
ID=27456771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP1999/001100 WO1999046040A1 (fr) | 1998-03-09 | 1999-03-08 | Catalyseur pour l'extraction d'hydrocarbures de gaz d'echappement et procede de clarification de gaz d'echappement |
Country Status (5)
Country | Link |
---|---|
US (4) | US6602481B1 (ja) |
EP (2) | EP1063010B1 (ja) |
DE (1) | DE69939011D1 (ja) |
DK (1) | DK1063010T3 (ja) |
WO (1) | WO1999046040A1 (ja) |
Cited By (2)
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US7364712B2 (en) | 2000-11-17 | 2008-04-29 | Osaka Gas Company Limited | Catalyst for purifying methane-containing waste gas and method of purifying methane-containing waste gas |
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Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1063010B1 (en) * | 1998-03-09 | 2008-07-02 | Osaka Gas Company Limited | Method for removing methane from exhaust gas |
KR100392943B1 (ko) * | 2001-05-16 | 2003-07-28 | (주)케이에이치 케미컬 | 디젤엔진 배기가스의 정화용 촉매 |
JP3870783B2 (ja) * | 2001-12-27 | 2007-01-24 | 日産自動車株式会社 | 燃料電池自動車用排ガス浄化システムおよび燃料電池自動車の排ガスの浄化方法 |
WO2005092495A1 (en) | 2004-03-29 | 2005-10-06 | Showa Denko K.K. | Palladium, tungsten and zirconium-based catalyst for production of oxygen-containing compound, production process of the catalyst, and production process of oxygen-containing compound using the catalyst |
US7601671B2 (en) * | 2004-10-28 | 2009-10-13 | Umicore Ag & Co. Kg | Drying method for exhaust gas catalyst |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6051543A (ja) * | 1983-08-31 | 1985-03-23 | Mitsubishi Heavy Ind Ltd | 酸化触媒 |
JPH08229353A (ja) * | 1995-02-24 | 1996-09-10 | Riken Corp | 排ガス浄化材及び排ガス浄化方法 |
JPH1033985A (ja) * | 1996-07-19 | 1998-02-10 | Ict:Kk | ディーゼルエンジン排ガス浄化用触媒 |
Family Cites Families (63)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2911357A (en) * | 1955-12-30 | 1959-11-03 | Phillips Petroleum Co | Catalysts for the conversion and reforming of hydrocarbons comprising a platinum group metal with a stabilizing metal |
US3481787A (en) * | 1964-06-11 | 1969-12-02 | Engelhard Ind Inc | Fuel cell comprising a raney catalyst alloy consisting of platinum and a member selected from the group consisting of zirconium,tungsten and rhenium |
US4053556A (en) * | 1971-06-16 | 1977-10-11 | Johnson, Matthey & Co., Limited | Catalysis |
US3988423A (en) * | 1974-10-11 | 1976-10-26 | Sumitomo Chemical Company, Limited | Method for removing harmful materials from waste gas |
JPS55155739A (en) * | 1979-05-23 | 1980-12-04 | Toyota Central Res & Dev Lab Inc | Exhaust gas purifying catalyzer |
US4366668A (en) * | 1981-02-25 | 1983-01-04 | Gulf Research & Development Company | Substoichiometric combustion of low heating value gases |
FR2521448A1 (fr) * | 1982-02-15 | 1983-08-19 | Inst Francais Du Petrole | Procede pour l'hydrodesulfuration de gaz naturel contenant des composes organiques du soufre et de l'oxygene |
US4844837A (en) * | 1982-09-30 | 1989-07-04 | Engelhard Corporation | Catalytic partial oxidation process |
US4572904A (en) * | 1983-09-27 | 1986-02-25 | Signal Applied Technologies Inc. | Lead-tolerant catalyst system for treating exhaust gas containing lead compounds |
JPS6133233A (ja) * | 1984-07-25 | 1986-02-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | メタン系燃料の燃焼用触媒およびそれを用いた燃焼方法 |
JPH0352672Y2 (ja) * | 1987-08-03 | 1991-11-15 | ||
US4921830A (en) * | 1988-04-13 | 1990-05-01 | Phillips Petroleum Company | Catalyst for the oxidation of carbon monoxide |
CA1334962C (en) * | 1988-04-14 | 1995-03-28 | Tomohisa Ohata | Catalyst for purifying exhaust gas and method for production thereof |
US4916108A (en) * | 1988-08-25 | 1990-04-10 | Westinghouse Electric Corp. | Catalyst preparation using supercritical solvent |
US5061464A (en) * | 1988-11-14 | 1991-10-29 | Johnson Matthey, Inc. | Oxidation process and catalyst for use therefor |
FR2646843B1 (fr) * | 1989-05-10 | 1991-12-13 | Rhone Poulenc Chimie | Zircone microporeuse et son procede de preparation |
US5141912A (en) * | 1989-06-28 | 1992-08-25 | W. R. Grace & Co.-Conn. | Chrome/platinum/palladium catalyst for hydrocarbon emission control |
US5106800A (en) * | 1989-11-20 | 1992-04-21 | Uop | Method of stabilizing a reforming catalyst |
US5232890A (en) * | 1990-01-02 | 1993-08-03 | Ganguli Partha S | Precious metal catalysts with oxygen-ion conducting support |
JP3113662B2 (ja) * | 1990-02-26 | 2000-12-04 | 株式会社日本触媒 | ディーゼルエンジン排ガス浄化用触媒体 |
US5259754A (en) * | 1990-11-26 | 1993-11-09 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
DE69130225T2 (de) * | 1990-11-26 | 1999-04-08 | Catalytica Inc | Mehrstufenverfahren für die verbrennung von brennstoffmischungen |
US5128291A (en) * | 1990-12-11 | 1992-07-07 | Wax Michael J | Porous titania or zirconia spheres |
JP2848970B2 (ja) * | 1990-12-21 | 1999-01-20 | 日本碍子株式会社 | ハニカムヒーター及び触媒コンバーター |
EP0494388B1 (en) * | 1991-01-08 | 1995-12-06 | Agency Of Industrial Science And Technology | Process for removing nitrogen oxides from exhaust gases |
US5145825A (en) | 1991-04-08 | 1992-09-08 | Engelhard Corporation | Oxidation catalyst resistant to sulfation |
GB9108656D0 (en) * | 1991-04-23 | 1991-06-12 | Shell Int Research | Process for the preparation of a catalyst or catalyst precursor |
US5260043A (en) | 1991-08-01 | 1993-11-09 | Air Products And Chemicals, Inc. | Catalytic reduction of NOx and carbon monoxide using methane in the presence of oxygen |
US5191139A (en) * | 1991-11-04 | 1993-03-02 | Texaco Chemical Company | Process for oligomerizing olefins using sulfate-activated group IV oxides |
CA2103876A1 (en) * | 1992-08-27 | 1994-02-28 | Stuart Leon Soled | Group viii metal containing tungsten oxide silica modified zirconia as acid catalyst |
US5856263A (en) * | 1992-08-28 | 1999-01-05 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts comprising substantially pure alpha-alumina carrier for treating exhaust gases |
EP0605251A1 (en) | 1992-12-28 | 1994-07-06 | Kabushiki Kaisha Riken | Exhaust gas cleaner |
JPH06246159A (ja) * | 1993-02-25 | 1994-09-06 | Osaka Gas Co Ltd | ガスエンジン排ガス浄化用三元触媒及びガスエンジン排ガスの浄化方法 |
CA2138133C (en) * | 1993-04-28 | 2002-04-23 | Kazuo Tsuchitani | Method for removal of nitrogen oxides from exhaust gas |
JPH0760117A (ja) * | 1993-08-30 | 1995-03-07 | Honda Motor Co Ltd | 排気ガス浄化用触媒 |
US5447898A (en) * | 1993-09-21 | 1995-09-05 | Shell Oil Company | Process for the preparation of zirconia |
TW299307B (ja) * | 1993-11-29 | 1997-03-01 | Shell Internat Res Schappej Bv | |
US5629257A (en) * | 1994-01-21 | 1997-05-13 | Sun Company, Inc. (R&M) | Solid superacid catalysts comprising platinum metal |
US5451558A (en) * | 1994-02-04 | 1995-09-19 | Goal Line Environmental Technologies | Process for the reaction and absorption of gaseous air pollutants, apparatus therefor and method of making the same |
US6284210B1 (en) * | 1994-11-15 | 2001-09-04 | Institut Francais Du Petrole | Combustion catalyst and combustion process using such a catalyst |
US6497851B1 (en) * | 1994-12-06 | 2002-12-24 | Englehard Corporation | Engine exhaust treatment apparatus and method of use |
GB9511412D0 (en) | 1995-06-06 | 1995-08-02 | Johnson Matthey Plc | Improvements in emission control |
US5741467A (en) * | 1995-06-07 | 1998-04-21 | Asec Manufacturing | Palladium catalyst washcoat supports for improved methane oxidation in natural gas automotive emission catalysts |
US5720931A (en) * | 1995-07-21 | 1998-02-24 | Guild Associates, Inc. | Catalytic oxidation of organic nitrogen-containing compounds |
US5707920A (en) * | 1995-12-08 | 1998-01-13 | Exxon Research And Engineering Company | Isobutanol synthesis catalyst |
FR2742680B1 (fr) * | 1995-12-22 | 1998-01-16 | Inst Francais Du Petrole | Catalyseur de combustion et procede de combustion utilisant un tel catalyseur |
US5837641A (en) * | 1996-01-16 | 1998-11-17 | Uop Llc | Method of promoting the activity of solid strong acid catalysts |
US5905180A (en) * | 1996-01-22 | 1999-05-18 | Regents Of The University Of Minnesota | Catalytic oxidative dehydrogenation process and catalyst |
US5786294A (en) * | 1996-05-10 | 1998-07-28 | Northwestern University | Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure |
JPH1052628A (ja) | 1996-06-07 | 1998-02-24 | Toyota Motor Corp | ディーゼルエンジンの排ガス浄化用触媒装置 |
US5830421A (en) * | 1996-07-03 | 1998-11-03 | Low Emissions Technologies Research And Development Partnership | Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process |
GB9622911D0 (en) * | 1996-11-04 | 1997-01-08 | Bp Chem Int Ltd | Process |
US5753192A (en) * | 1996-11-29 | 1998-05-19 | Ford Global Technologies, Inc. | Zirconia and sulfate in NOx traps to improved trapping and sulfur tolerance |
IT1289934B1 (it) * | 1997-02-20 | 1998-10-19 | Eniricerche Spa | Catalizzatore superacido per la idroisomerizzazione di n-paraffine e procedimento per la sua preparazione |
US6110861A (en) * | 1997-06-02 | 2000-08-29 | The University Of Chicago | Partial oxidation catalyst |
US6348430B1 (en) * | 1997-06-20 | 2002-02-19 | Degussa Ag | Exhaust gas treatment catalyst for internal combustion engines with two catalytically active layers on a carrier structure |
US5994257A (en) * | 1997-08-12 | 1999-11-30 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
US6139814A (en) * | 1997-11-10 | 2000-10-31 | Ford Global Technologies, Inc. | Thermally stable, high-surface-area metal oxides made by organic templating |
US5895636A (en) * | 1997-12-02 | 1999-04-20 | Engelhard Corporation | Catalytic compositions and methods for suppression of halogenation of organic compounds with oxidation products of halogenated organic compounds in gaseous emission streams |
EP1063010B1 (en) * | 1998-03-09 | 2008-07-02 | Osaka Gas Company Limited | Method for removing methane from exhaust gas |
JP4029233B2 (ja) * | 1998-05-11 | 2008-01-09 | 第一稀元素化学工業株式会社 | セリウム−ジルコニウム系複合酸化物及びその製造方法ならびに排ガス浄化用触媒材料 |
DE19826082A1 (de) | 1998-06-12 | 1999-12-16 | Tils Peter | Verfahren zum Verpacken von zu entsorgendem Gut wie beispielsweise Hausmüll oder Speiseresten |
JP3559858B2 (ja) * | 2000-02-07 | 2004-09-02 | 東ソー株式会社 | 有機化合物燃焼除去触媒および燃焼除去法 |
-
1999
- 1999-03-08 EP EP99939143A patent/EP1063010B1/en not_active Expired - Lifetime
- 1999-03-08 DK DK99939143T patent/DK1063010T3/da active
- 1999-03-08 US US09/622,469 patent/US6602481B1/en not_active Expired - Fee Related
- 1999-03-08 EP EP05020014A patent/EP1611950A1/en not_active Withdrawn
- 1999-03-08 WO PCT/JP1999/001100 patent/WO1999046040A1/ja active IP Right Grant
- 1999-03-08 DE DE69939011T patent/DE69939011D1/de not_active Expired - Lifetime
-
2003
- 2003-06-12 US US10/459,963 patent/US6887446B2/en not_active Expired - Fee Related
-
2004
- 2004-05-04 US US10/838,552 patent/US7371706B2/en not_active Expired - Fee Related
- 2004-07-22 US US10/896,507 patent/US20050002839A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6051543A (ja) * | 1983-08-31 | 1985-03-23 | Mitsubishi Heavy Ind Ltd | 酸化触媒 |
JPH08229353A (ja) * | 1995-02-24 | 1996-09-10 | Riken Corp | 排ガス浄化材及び排ガス浄化方法 |
JPH1033985A (ja) * | 1996-07-19 | 1998-02-10 | Ict:Kk | ディーゼルエンジン排ガス浄化用触媒 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1063010A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7364712B2 (en) | 2000-11-17 | 2008-04-29 | Osaka Gas Company Limited | Catalyst for purifying methane-containing waste gas and method of purifying methane-containing waste gas |
US10112178B2 (en) | 2015-03-05 | 2018-10-30 | Shell Oil Company | Methane oxidation catalyst, process to prepare the same and method of using the same |
US10512896B2 (en) | 2015-03-05 | 2019-12-24 | Shell Oil Company | Methane oxidation catalyst, process to prepare the same and method of using the same |
Also Published As
Publication number | Publication date |
---|---|
US7371706B2 (en) | 2008-05-13 |
US6602481B1 (en) | 2003-08-05 |
DK1063010T3 (da) | 2008-09-15 |
US6887446B2 (en) | 2005-05-03 |
EP1063010A1 (en) | 2000-12-27 |
US20040235654A1 (en) | 2004-11-25 |
DE69939011D1 (de) | 2008-08-14 |
EP1611950A1 (en) | 2006-01-04 |
EP1063010A4 (en) | 2002-09-18 |
US20050002839A1 (en) | 2005-01-06 |
EP1063010B1 (en) | 2008-07-02 |
US20040013592A1 (en) | 2004-01-22 |
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