WO2009131118A1 - 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ - Google Patents
排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ Download PDFInfo
- Publication number
- WO2009131118A1 WO2009131118A1 PCT/JP2009/057915 JP2009057915W WO2009131118A1 WO 2009131118 A1 WO2009131118 A1 WO 2009131118A1 JP 2009057915 W JP2009057915 W JP 2009057915W WO 2009131118 A1 WO2009131118 A1 WO 2009131118A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- catalyst
- gas purification
- composite oxide
- poisoning
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title claims description 5
- 239000008199 coating composition Substances 0.000 title 1
- 239000000243 solution Substances 0.000 claims description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 9
- 150000002602 lanthanoids Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052768 actinide Inorganic materials 0.000 claims description 3
- 150000001255 actinides Chemical class 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000007789 gas Substances 0.000 abstract description 40
- 238000002485 combustion reaction Methods 0.000 abstract description 34
- 231100000572 poisoning Toxicity 0.000 abstract description 28
- 230000000607 poisoning effect Effects 0.000 abstract description 28
- 230000008859 change Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000020169 heat generation Effects 0.000 abstract description 2
- 239000013618 particulate matter Substances 0.000 description 59
- 230000000694 effects Effects 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 31
- 208000005374 Poisoning Diseases 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000843 powder Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 229910052777 Praseodymium Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- -1 ammonium carbonate compound Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 101100224414 Caenorhabditis elegans dpf-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001507939 Cormus domestica Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006219 ZrO(NO3)2·2H2O Inorganic materials 0.000 description 1
- GWGQWFHTAOMUBD-UHFFFAOYSA-N [[3-[bis(phosphonomethyl)amino]-2-hydroxypropyl]-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CC(O)CN(CP(O)(O)=O)CP(O)(O)=O GWGQWFHTAOMUBD-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/0215—Coating
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0478—Surface coating material on a layer of the filter
-
- 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
- B01D2255/1021—Platinum
-
- 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
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/10—Carbon or carbon oxides
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an exhaust gas purification catalyst comprising a composite oxide suitable for burning PM (particulate matter) emitted from a diesel engine such as an automobile, a method for producing the same, and a paint for the catalyst using the same
- the present invention relates to a diesel exhaust gas purification filter in which
- particulates mainly composed of nitrogen oxides (NO x ) and carbon (hereinafter also referred to as “PM”) are contained in the exhaust gas, which causes environmental pollution.
- PM nitrogen oxides
- PM carbon
- a diesel particulate filter (DPF) made of porous ceramic is installed in an exhaust gas flow path to trap PM.
- PM is accumulated in the DPF, the DPF can be regenerated to a state before the PM collection by removing the PM by burning the collected PM intermittently or continuously.
- a method of burning PM by forced heating from the outside such as an electric heater or a burner, installing an oxidation catalyst on the engine side of DPF, and converting NO contained in exhaust gas into NO 2 by the oxidation catalyst
- a method of burning PM by the oxidizing power of NO 2 is used.
- PM combustion catalyst for burning and removing PM trapped in DPF
- Pt of a catalyst metal is supported on alumina or the like having a high specific surface area.
- Pt has a low catalytic activity of burning PM at exhaust gas temperature level, it is considered difficult to burn PM continuously using the heat of the exhaust gas. That is, forced heating means from the outside is required. Further, Pt is expensive, which causes a problem of cost increase.
- Patent Documents 1 to 3 disclose a mixture containing Ce and Bi or a transition metal element as an oxidation catalyst based on a composite oxide of ceria which does not contain a noble metal element such as Pt.
- a noble metal element such as Pt.
- complex oxides consisting only of Ce and Bi, or Ce and Bi and transition metal elements the melting point of Bi is low, and therefore, when exposed to high temperatures of about 800 ° C. for a long time, liberation of Bi occurs and the catalytic activity decreases. Do. For this reason, further improvement is desired regarding heat resistance.
- a composite oxide containing Ce and Bi is excellent in catalytic activity to lower the PM combustion initiation temperature.
- the catalyst activity decreases.
- the present invention has been made in view of the problems of the prior art, and the object of the present invention is to provide a high specific surface area and heat resistance as compared with the conventional composite oxide containing Ce and Bi. It is an object of the present invention to provide a composite oxide for an exhaust gas purification catalyst which is excellent and has high resistance to S poisoning, a method for producing the same, a paint for an exhaust gas purification catalyst and a filter for diesel exhaust gas purification.
- an exhaust gas purification catalyst is composed of a composite oxide obtained by adding a predetermined element to Ce and Bi, and has completed the present invention.
- the composite oxide for exhaust gas purification catalyst of the present invention is Ce, Bi, R (wherein R is one or more of lanthanoids except La, Ce) and R '(where R' is group 3 or 4 or 13). Or a composite oxide for an exhaust gas purification catalyst composed of an element selected from group 14).
- the present invention also provides a paint containing the composite oxide for an exhaust gas purification catalyst, and a DPF in which the paint is applied to a porous filter.
- a complex oxide obtained by adding the above R and R 'elements to Ce, Bi has a high specific surface area, and can avoid sintering between particles even at high temperatures, and it is possible to prevent BET even when exposed to high temperatures. There is little decline. That is, since liberation of Bi can be suppressed even at a high temperature, there is an effect that a catalyst excellent in heat resistance can be obtained.
- the fact that the specific surface area is high and the change is small means that more S adsorption is possible, and it is possible to suppress the decrease in catalytic activity due to S poisoning.
- the fact that the decrease in the catalyst activity due to the heat resistance and the S poisoning is small leads to the advantage of the exhaust gas purification system itself that the catalyst can be used for a long time in the same state. Moreover, the advantage that the frequency
- the composite oxide for exhaust gas purification catalyst of the present invention is a composite oxide containing Ce, Bi and at least four elements of R and R ′.
- R is one or more elements of a lanthanoid except La and Ce
- R ′ is at least one or more elements selected from Group 3 or 4 or 13 or 14 groups.
- z it is preferable that 0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 1.0, and 0 ⁇ z ⁇ 0.5. Outside this range, in the case of 0.4 ⁇ x, Bi does not enter the crystal lattice and the heat resistance is lowered. Also, in the case of 1.0 ⁇ y, 0.5 ⁇ z, heterophases may be generated and an activity derived from a complex oxide mainly composed of Ce atoms may not be obtained.
- Bi, R, or R ' which does not substitute Ce of a cerium oxide structure may exist as an impurity phase in complex oxide, and as long as the effect of the present invention is not inhibited, the existence of the impurity phase Is acceptable.
- the molar ratio of the complex oxide as a whole including Ce, Bi, R, or R ′ in the impurity phase may satisfy the above.
- the complex oxide of the present invention is a complex oxide based on Ce, Bi, the mechanism of catalytic activity that can burn PM from low temperature is considered in the conventional Ce-Bi complex oxide It is considered to be similar to the mechanism
- the cation in the composite oxide mainly composed of Ce atom causes an apparent valence change, and the Ce site is substituted by an atom whose ion radius is different from that of Ce, such as Bi, R, R ' It is thought that the active oxygen necessary for oxidation can be easily supplied from a relatively low temperature region by the state in which oxygen in the lattice is easily released out of the lattice due to the lattice distortion caused by this.
- the lattice strain due to substitution and the presence of R stabilize the presence of Bi atoms in the crystal lattice and bring about the effect of preventing the liberation of Bi.
- Bi exhibits an action of improving the catalytic activity in a low temperature range, that is, a action of reducing the combustion initiation temperature of PM.
- the mechanism is considered as described above. Even if the additive amount of Bi is relatively small, the catalytic activity in the low temperature range is improved. However, if the amount of addition of Bi is too high, the effect is not improved, but there is a risk that the catalyst substance may melt when exposed to high temperature.
- the melting point of the composite oxide is lowered by the addition of Bi having a low melting point.
- the propriety of the amount of addition of Bi can be known by the combustion start temperature of PM in a sample after being exposed to high temperature for a long time, and the change of the crystal structure. As examined based on such evaluations, it is preferable that the blending ratio of Bi in the composite oxide be in the range of 0 ⁇ x ⁇ 0.4 as described above. When x exceeds 0.4, the PM combustion start temperature of the sample after exposure to high temperature for a long time rises.
- Bi atoms are liberated from the fluorite structure to easily form heterophases such as Bi oxide or a composite oxide of Bi and an additive element, and contain an impurity phase in an amount that inhibits the effects of the present invention. May become a complex oxide.
- R one or more of lanthanoids except La and Ce
- R ′ groups 3, 4, 13 and 14 excluding lanthanoids and actinoids
- the present invention provides a novel composite oxide to which elements (elements of a species or more) are added. Even if the amount of R and R 'added is relatively small, an excellent heat resistance improvement effect can be obtained. Even if the addition amount of the third and fourth elements increases, the heat resistance improvement effect is generally maintained.
- the blending ratio of R may be in the range of 0 ⁇ y ⁇ 1.0 as described above. However, when the blending ratio of R increases, the combustion start temperature of PM tends to increase, so 0 ⁇ y ⁇ 0.5 is more preferable.
- R is composed of a lanthanoid except La and Ce.
- a lanthanoid having a fluorite type structure similar to that of cerium oxide (CeO 2 ) as an oxide By substituting a part of the Ce atoms with such an element, the fluorite structure can be easily maintained, and an exhaust gas purification catalyst with further improved heat resistance can be obtained.
- this type of element include Pr and Tb. It is desirable that one or two of Pr and Tb be contained as R, and it is more preferable that all of R be composed of one or two of Pr and Tb. Particularly, Pr is preferable in achieving a balance between the decrease in PM combustion start temperature and the improvement in heat resistance in a well-balanced manner.
- R ' is group 3 (Sc, Y), group 4 (Ti, Zr, Hf, Rf), group 13 (B, Al, Ga, In, Tl), group 14 (C, Si, Ge) excluding lanthanoids and actinoids , Sn, Pb) is composed of one or more elements.
- an element which has an effect of suppressing sintering of primary particles at the time of firing and is effective in increasing the specific surface area of the composite oxide is preferable.
- it is Zr, Al, Y, Si or the like.
- An increase in specific surface area leads to an increase in catalytic activity, which increases the tolerance for S poisoning. This is because the amount of sulfur required to cover the particle surface is increased.
- platinum group elements have the function of promoting the oxidation of fuel contained in exhaust gas and unburned components such as NO and CO. Further, the effect of further lowering the PM combustion start temperature can also be expected.
- platinum group elements Pt, Rh, Pd, Ir, Ru, Os
- Pt, Rh, and Pd are particularly effective in enhancing the catalytic efficiency.
- the platinum group element can be made to coexist, for example, in the form of being contained in the complex oxide of the present invention.
- the complex oxidation of the present invention is carried out by incorporating a platinum group element in a substance generally used as a catalyst support such as Al 2 O 3 , TiO 2 , SiO 2 and mixing the substance with the complex oxide of the present invention.
- platinum group elements can coexist.
- the amount of the platinum group element is, for example, the content of the platinum group element in the complex oxide of the present invention, or in the mixture of the complex oxide of the present invention and the catalyst support substance when the catalyst support substance is further mixed. It may be 0.05 to 5% by mass.
- heat resistance As a method of evaluating the heat resistance when the PM combustion catalyst receives a high temperature / long-term heat history, for example, a process of heating the complex oxide synthesized by calcination in the air at high temperature for a long time (hereinafter referred to as “heat resistance It is effective to view how much the catalytic activity for PM changes between immediately after being subjected to the treatment and after being subjected to the heat treatment and after being subjected to the heat treatment.
- the catalytic activity for PM can be evaluated, for example, by the PM combustion temperature described later.
- the composite oxide before being subjected to the above heat treatment is only subjected to a heat history of 800 ° C. for 2 hours.
- the difference between the PM burning temperature of the sample subjected to the heat treatment at 800 ° C. for 100 hours and the PM burning temperature of the sample before the heat treatment is given to the sample subjected to the heat history of 800 ° C. for 2 hours.
- the heat resistance index ⁇ T (° C.) is used.
- the low S poisoning rate means that the catalyst activity does not decrease for a long time even under a sulfur environment.
- the S degradation rate (SRd) the ratio of the catalyst activity (° C) after 5 hours of S poisoning to the catalyst activity (° C) immediately after the synthesis and 10 hours after S poisoning to the catalyst activity (° C) immediately after the synthesis
- SRd the average of the ratio of catalytic activity (° C) of
- the large S deterioration rate (SRd) means that the change rate by poisoning to the catalyst activity immediately after the synthesis is large.
- the S degradation rate (SRd) is expressed by equation (2) when it is expressed by the same variables as described above. ... (2)
- the inventors have synthesized the composite oxide of Ce, Bi, and composite oxides containing a third element and a fourth element at a temperature of 800 ° C. for 2 hours, and synthesized the oxide structure after the heat treatment, and the heat resistance.
- the relationship between the sex index ⁇ T, the S poisoning speed, and the S deterioration rate was investigated.
- the addition of the third element and the fourth element resulted in a high BET value immediately after synthesis, and a small change in the BET value after heat treatment, and the heat resistance index ⁇ T was accordingly small.
- the poisoning rate due to sulfur is also slow in S poisoning and that the S degradation rate can be reduced.
- the composite oxide to be the subject of the present invention can be suitably synthesized by a method of calcining a precipitated product obtained by a wet method.
- a water-soluble salt of Ce, a water-soluble salt of Bi, a water-soluble salt of R (for example, Pr), and a water-soluble salt of R '(for example, Al) are precipitated by a precipitant and oxidized by blowing in air.
- the precipitate is dried to form a "precursor", and the precursor is heat-treated to synthesize a composite oxide.
- precipitation is carried out in an aqueous solution in which a water-soluble salt of Ce (eg, nitrate), a water-soluble salt of Bi (eg, nitrate), a water-soluble salt of R (eg, nitrate), and a water-soluble salt of R '
- a water-soluble salt of Ce eg, nitrate
- Bi eg, nitrate
- R eg, nitrate
- R ' water-soluble salt of R '
- the upper limit of the ion concentration of Ce, Bi, R, R 'in the solution for forming a precipitate is determined by the solubility. However, if the concentration in the liquid is too high, reaction may not occur uniformly during stirring and may be uneven, and the load on the device may be excessive during stirring, which is not preferable.
- an alkali hydroxide and an alkali carbonate there is preferable to use any one or both of an alkali hydroxide and an alkali carbonate.
- sodium hydroxide or ammonia water as alkali hydroxide carbonated water such as carbonated water, carbon dioxide gas, sodium carbonate, potassium carbonate, sodium hydrogen carbonate as alkali carbonate, ammonia and the like, ammonia
- carbonated water such as carbonated water, carbon dioxide gas, sodium carbonate, potassium carbonate, sodium hydrogen carbonate as alkali carbonate, ammonia and the like
- ammonia It is preferable to use a mixture of water or ammonium water-soluble salts, or an ammonium carbonate compound having both functions, specifically, ammonium carbonate, ammonium hydrogen carbonate and the like.
- the salt solution contains urea and this salt solution is heated to decompose the urea to generate ammonia, thereby making the salt solution alkaline to obtain a precipitate.
- the pH of the solution when forming a precipitate should be controlled in the range of 6-11. If the pH is less than 6, it is not preferable because Bi, Ce, R and R 'may not be coprecipitated.
- compounds that can be hydrolyzed are prepared as a Ce compound, a Bi compound, an R compound, and an R 'compound, respectively, and these are added to water to hydrolyze, thereby forming a mixed sol, aggregation, and precipitation.
- the hydrolyzable compound for example, alkoxides of the respective metal elements and ⁇ -keto acid salts can be mentioned.
- the obtained precipitate is filtered, washed with water, and dried by vacuum drying, ventilation drying, etc., as a precursor.
- it can be made to dry-process as it is immediately after filtering, or it can be made to dry-process, after granulating to a predetermined shape.
- the precursor is heat-treated (calcined) at, for example, 400 to 1000 ° C., preferably 500 to 850 ° C., in the powder form or in a granulated state, to synthesize a target complex oxide.
- the atmosphere at the time of firing is not particularly limited as long as the composite oxide can be formed, and, for example, an atmosphere in air, nitrogen, argon, and a combination of these with water vapor can be used.
- a platinum group element is contained in the composite oxide of the present invention
- a method is employed in which the fired composite oxide is impregnated with a salt or complex containing a target amount of platinum group element, and then dried and fired. it can.
- a paint for an exhaust gas purification catalyst and a DPF using the same can be constructed using the complex oxide of the present invention as an exhaust gas purification catalyst.
- the paint for exhaust gas purification catalyst is a paint for the exhaust gas purification catalyst of the present invention and a solvent and an inorganic binder.
- a dispersant, a viscosity modifier, or a pH adjuster may be included.
- a polar solvent or a nonpolar solvent may be used.
- a solvent having a low boiling point is preferable for quick drying, but a water-based solvent may be used in consideration of handling. Specifically, water, isopropyl alcohol, terpineol, 2-octanol, butyl carbitol acetate and the like can be suitably used.
- the powder such as Al 2 O 3, TiO 2, SiO 2 is preferably used. Since the PM catalyst is exposed to high temperatures, materials exhibiting stable properties even at high temperatures are preferred.
- FIG. 1 shows an example of the DPF.
- the DPF 1 has a tubular form in which the cross section viewed from the inlet side 10 has a honeycomb structure, and the material is made of porous ceramic.
- the inlet side (also referred to as “engine side”) 10 and the outlet side (also referred to as “air open side”) 11 do not have a direct through hole, and a porous ceramic is a filter.
- a porous ceramic is a filter.
- ceramic, cordierite, silicon carbide, aluminum titanate and the like are suitably used as the porous ceramic.
- the shape may be foam, mesh or plate.
- the composite oxide of the present invention may be located on the engine side 10 of the DPF. Since the catalyst is a PM catalyst, the PM combustion temperature can not be reduced unless it is on the engine side where PM accumulates.
- a platinum-based catalyst may be disposed on the air release side from the PM catalyst of the present invention.
- a multilayer catalyst structure in which a platinum-based catalyst layer and a PM catalyst layer of the present invention are separately applied to the wall surface 12 of the DPF on the engine side may be separately applied.
- the paint for exhaust gas purification catalyst of the present invention may be applied to the wall surface 12 on the engine side, and the paint for platinum-based catalyst may be applied to the wall surface 14 on the air release side.
- the PM catalyst 30 is disposed on the engine side
- the platinum-based catalyst 40 is disposed on the air release side.
- the platinum-based catalyst powder may be mixed with the paint for exhaust gas purification catalyst of the present invention and then applied.
- the platinum-based catalyst refers to a catalyst using a platinum group element.
- Example 1 Cerium nitrate hexahydrate as Ce source (Ce (NO 3) 3 ⁇ 6H 2 O), were prepared bismuth nitrate pentahydrate (Bi (NO 3) 3 ⁇ 5H 2 O) as a Bi source.
- a powder of rare earth oxide Pr oxide as an R source was dissolved in a concentrated nitric acid solution to prepare a nitric acid solution of R.
- aluminum nitrate nonahydrate (Al (NO 3 ) 3 .9H 2 O) as an R ′ source is prepared by mixing Ce, Bi, Pr, R ′ in a molar ratio of 0.50: 0.09: 0.39: 0. It mixed by the mixture ratio used as 01, and water was added so that the sum total of Ce, Bi, R, and R 'in mixed nitric acid solution might be 0.2 mol / L, and the raw material solution was obtained. The above raw material solution was added while stirring an aqueous solution of NaOH as a precipitant to obtain a precipitate of hydroxide. Thereafter, air was blown sufficiently in a high temperature of 70 ° C. or more to stabilize the hydroxide as an oxide.
- the resulting precipitate was filtered, washed with water and dried at 125 ° C. for about 15 hours to obtain a dry powder.
- the obtained powder is called a precursor.
- this precursor was calcined at 800 ° C. for 2 hours in the air atmosphere to obtain a composite oxide containing Ce, Bi and Pr as main components.
- Example 2 Cerium nitrate hexahydrate as Ce source in the same manner as in Example 1 (Ce (NO 3) 3 ⁇ 6H 2 O), bismuth nitrate pentahydrate as Bi sources (Bi (NO 3) 3 ⁇ 5H 2 O) Prepared.
- a powder of rare earth oxide Pr oxide as an R source was dissolved in a concentrated nitric acid solution to prepare a nitric acid solution of R.
- Example 3 Cerium nitrate hexahydrate as Ce source in the same manner as in Example 1 (Ce (NO 3) 3 ⁇ 6H 2 O), bismuth nitrate pentahydrate as Bi sources (Bi (NO 3) 3 ⁇ 5H 2 O) Prepared.
- a powder of rare earth oxide Pr oxide as an R source was dissolved in a concentrated nitric acid solution to prepare a nitric acid solution of R.
- a nitric acid solution of each of the above nitrates and R is mixed at a blending ratio such that the molar ratio of Ce, Bi, R is 0.5: 0.1: 0.4, and Ce, Bi, R in the mixed nitric acid solution
- Water was added to a total of 0.2 mol / L to obtain a raw material solution.
- an aqueous ammonium carbonate solution was added as a precipitant.
- the resulting precipitate was filtered, washed with water and dried at 125 ° C. for about 15 hours to obtain a dry powder.
- the obtained powder is called a precursor.
- this precursor was calcined at 800 ° C. for 2 hours in the air atmosphere to obtain a composite oxide containing Ce, Bi and Pr as main components.
- a nitric acid solution of each of the above nitrates and R is mixed at a blending ratio such that the molar ratio of Ce, Bi, R is 0.5: 0.1: 0.4, and Ce, Bi, R in the mixed nitric acid solution
- Water was added to a total of 0.2 mol / L to obtain a raw material solution. While stirring this solution, sodium hydroxide was added as a precipitant. Thereafter, under the same process and conditions as in Comparative Example 1, a composite oxide containing Ce, Bi and Pr as main components was obtained.
- the weight change curve (TG curve) and the differential thermal curve (DTA curve) are schematically shown in FIG.
- DTA curve the point at which the calorific value is maximum is taken as the PM combustion temperature. In the figure, the temperature is 50.
- ⁇ T was calculated from the difference between the PM combustion temperature (shown as 800 ° C. ⁇ 2 h) of the sample after heat treatment and the PM combustion temperature (shown as 800 ° C. ⁇ 100 h) before the heat treatment. This is called " ⁇ T heat resistance”.
- S poisoning speed (SV) was determined based on the equation (1).
- Table 1 shows the additive element molar ratio, the specific surface area, the PM combustion temperature, the S poisoning rate, and the S deterioration rate for the composite oxides of Examples 1 to 3 and Comparative Examples 1 to 3.
- Comparative Example 2 is the same production method as the catalyst of the present invention, and is a sample without R ′.
- R ′ is Y
- Example 1 (R'is Al), and Example 3 (R'is Zr), even after heat treatment, respectively 38.4m 2 / g and 32.3m 2 / g Showed a BET of 30 m 2 / g or more.
- Comparative Example 1 and Comparative Example 2 have the same composition and show the difference between the precipitating agent whether it is ammonium carbonate (Comparative Example 1) or sodium hydroxide (Comparative Example 2). It is shown that it is preferable to use sodium hydroxide as an agent.
- Comparative Example 2 the influence of the S processing is shown with reference to the “ ⁇ T5H-S processing” and the “ ⁇ T10H-S processing”.
- Comparative Example 2 there is no data after 5 hours.
- Comparative Example 1 was 67 ° C.
- Examples 1 to 3 (19 ° C. to 29 ° C.) were all lower than 67 ° C.
- Examples 1 to 3 (42 ° C. to 71 ° C.) were lower than Comparative Example 1 (115 ° C.) and Comparative Example 2 (87 ° C.). That is, in Examples 1 to 3 where BET was large, deactivation due to poisoning was less likely to occur.
- the S poisoning rate represents the degree of loss of catalyst activity per hour in terms of combustion temperature. Therefore, receiving the above results, Examples 1 to 3 (4.9 ° C. to 6.0 ° C.) were lower than the results of the comparative example (8.7 ° C. and 12.4 ° C.).
- the S degradation rate is an index showing how much the degradation of the activity is with respect to the initial catalyst activity. This also reflects the above tendency, and Examples 1 to 3 (10 ° C. to 13 ° C.) were lower than the results of Comparative Examples 1 and 2 (28 ° C. and 24 ° C.).
- the present invention can be suitably used for an exhaust gas filter (DPF) of a diesel engine.
- DPF exhaust gas filter
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Filtering Materials (AREA)
- Paints Or Removers (AREA)
- Processes For Solid Components From Exhaust (AREA)
Abstract
Description
《複合酸化物の作製》
各実施例、比較例の複合酸化物を以下のようにして作製した。
〔実施例1〕
Ce源として硝酸セリウム六水和物(Ce(NO3)3・6H2O)、Bi源として硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を用意した。一方、R源として希土類酸化物Pr酸化物の粉末を濃硝酸溶液に溶解し、Rの硝酸溶液を用意した。
実施例1と同様にCe源として硝酸セリウム六水和物(Ce(NO3)3・6H2O)、Bi源として硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を用意した。一方、R源として希土類酸化物Pr酸化物の粉末を濃硝酸溶液に溶解し、Rの硝酸溶液を用意した。
実施例1と同様にCe源として硝酸セリウム六水和物(Ce(NO3)3・6H2O)、Bi源として硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を用意した。一方、R源として希土類酸化物Pr酸化物の粉末を濃硝酸溶液に溶解し、Rの硝酸溶液を用意した。
Ce源として硝酸セリウム六水和物(Ce(NO3)3・6H2O)、Bi源として硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を用意した。一方、R源として希土類酸化物Pr酸化物の粉末を濃硝酸溶液に溶解し、Rの硝酸溶液を用意した。
Ce源として硝酸セリウム六水和物(Ce(NO3)3・6H2O)、Bi源として硝酸ビスマス五水和物(Bi(NO3)3・5H2O)を用意した。一方、R源として希土類酸化物Pr酸化物の粉末を濃硝酸溶液に溶解し、Rの硝酸溶液を用意した。
得られた複合酸化物の耐熱性を評価するために、各複合酸化物の一部を、電気炉により空気中800℃で100時間にわたって熱処理(耐熱処理)した。
各実施例、比較例で得られた耐熱処理前の試料(800℃×2hと表示)、および上記耐熱処理後の試料(800℃×100hと表示)について、メノウ乳鉢で解粒し、粉末とした後、BET法により比表面積を求めた。測定はユアサイオニクス製の4ソーブUSを用いて行った。
各実施例、比較例で得られた試料、および上記耐熱処理後の試料について、カーボンブラックとの混合粉を作り、その中の一部を規定量分取した上、TG/DTA装置を用いてカーボンブラック燃焼温度を求めることによってPM燃焼開始温度を評価した。具体的には以下のようにした。
各実施例、比較例で得られた試料について、10Vol%の濃度のSO2ガスで流量500ml/minの環境に5時間と10時間放置させ被毒させた。その後それぞれの試料とカーボンブラックとの混合粉を作り、その中の一部を規定量分取した上、TG/DTA装置を用いてカーボンブラック燃焼温度を求めることによってPM燃焼温度を評価した。5時間被毒させた場合のPM燃焼温度と被毒前のPM燃焼温度との差を「ΔT5H-S処理」と呼び、10時間の場合を「ΔT10H-S処理」と呼ぶ。
(1)式に基づいてS被毒速度(SV)を求めた。
実施例1~3、比較例1~3の複合酸化物について、添加元素モル比、比表面積、PM燃焼温度、S被毒速度、S劣化率を表1に示す。
10 エンジン側
11 大気開放側
12 エンジン側壁面
14 大気開放側壁面
30 エンジン側壁面に塗布されたPM触媒
40 大気開放側壁面に塗布された白金系触媒
Claims (6)
- Ce、Bi、R(ただしRはLa、Ceを除くランタノイドの1種以上)およびR´(ただしR´はランタノイドとアクチノイドを除く3族、4族、13族から選ばれた1種以上の元素)で構成される排ガス浄化触媒用複合酸化物。
- 前記R´がAl、Zr、Yから選ばれた元素である請求項1に記載された排ガス浄化触媒用複合酸化物。
- 前記RはPrである請求項1または2のいずれかの請求項に記載された排ガス浄化触媒用複合酸化物。
- Ceの硝酸溶液と、Biの硝酸溶液と、前記Rの硝酸溶液と、前記R´の硝酸溶液を混合して混合液を得る工程と、
水酸化アルカリ及び/又は炭酸アルカリと前記混合液を合わせて沈殿物を得る工程を含む排ガス浄化触媒用複合酸化物の製造方法。 - 請求項1乃至3の何れかの請求項に記載された排ガス浄化触媒用複合酸化物を含む排ガス浄化触媒用塗料。
- 多孔質フィルタと、
前記多孔質フィルタ上に形成された、
請求項1乃至3の何れかの請求項に記載された排ガス浄化触媒用複合酸化物と、
無機バインダを含む排ガス浄化触媒層を有するディーゼル排ガス浄化用フィルタ。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009801148889A CN102015097A (zh) | 2008-04-23 | 2009-04-21 | 废气净化催化剂用复合氧化物及其制造方法以及废气净化催化剂用涂料和柴油机废气净化用过滤器 |
US12/935,701 US8304364B2 (en) | 2008-04-23 | 2009-04-21 | Complex oxide for exhaust gas purification catalyst, production method thereof, coating material for exhaust gas purification catalyst, and diesel exhaust gas purification filter |
EP09735657.0A EP2269730B1 (en) | 2008-04-23 | 2009-04-21 | Composite oxide for catalyst for exhaust gas purification, process for producing the same, catalyst for exhaust gas purification, and filter for diesel exhaust gas purification |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008112434 | 2008-04-23 | ||
JP2008-112434 | 2008-04-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009131118A1 true WO2009131118A1 (ja) | 2009-10-29 |
Family
ID=41216850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/057915 WO2009131118A1 (ja) | 2008-04-23 | 2009-04-21 | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ |
Country Status (6)
Country | Link |
---|---|
US (1) | US8304364B2 (ja) |
EP (1) | EP2269730B1 (ja) |
JP (1) | JP4416830B2 (ja) |
KR (1) | KR101574553B1 (ja) |
CN (2) | CN104759274A (ja) |
WO (1) | WO2009131118A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5528040B2 (ja) * | 2008-10-03 | 2014-06-25 | Dowaエレクトロニクス株式会社 | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ |
JP5973914B2 (ja) * | 2010-08-05 | 2016-08-23 | Dowaエレクトロニクス株式会社 | 排ガス処理用触媒組成物の製造方法 |
US9977874B2 (en) | 2011-11-07 | 2018-05-22 | Nike, Inc. | User interface for remote joint workout session |
CN103282907A (zh) | 2010-11-05 | 2013-09-04 | 耐克国际有限公司 | 自动个人训练的方法和系统 |
WO2016016127A1 (en) | 2014-07-29 | 2016-02-04 | Treibacher Industrie Ag | Noble metal-free catalyst compositions |
CN107970911B (zh) * | 2017-12-01 | 2020-10-13 | 南京云高新型材料有限公司 | 一种环保节能高转化率稀土催化剂及其制备方法 |
JP7358157B2 (ja) * | 2019-09-27 | 2023-10-10 | 日本碍子株式会社 | 複合酸化物触媒、多孔質複合体および複合酸化物触媒の製造方法 |
JP7379665B2 (ja) * | 2020-03-27 | 2023-11-14 | 京セラ株式会社 | 触媒、ハニカム構造体および排ガス浄化装置 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06211525A (ja) | 1992-09-15 | 1994-08-02 | Rhone Poulenc Chim | 酸化第二セリウムをベースにした組成物、製法及び用途 |
JPH06279027A (ja) * | 1993-02-10 | 1994-10-04 | Rhone Poulenc Chim | ジルコニウム及びセリウムの混合酸化物を基とする組成物、その合成方法並びに使用方法 |
JPH06315634A (ja) * | 1992-12-14 | 1994-11-15 | Sekiyu Sangyo Kasseika Center | 窒素酸化物接触還元用触媒構造体 |
JP2003238159A (ja) | 2001-12-11 | 2003-08-27 | Kinya Adachi | 低温酸化還元能を有する複合酸化物とその製造方法 |
WO2005085137A1 (ja) * | 2004-03-08 | 2005-09-15 | Anan Kasei Co., Ltd. | 複合酸化物 |
JP2005281021A (ja) * | 2004-03-29 | 2005-10-13 | Nobuhito Imanaka | 希土類複合酸化物 |
JP2006224032A (ja) | 2005-02-18 | 2006-08-31 | Toyota Motor Corp | 排ガス浄化用触媒 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2720296B1 (fr) * | 1994-05-27 | 1996-07-12 | Rhone Poulenc Chimie | Composés à base d'alumine, d'oxyde de cérium et d'oxyde de zirconium à réductibilité élevée, leur procédé de préparation et leur utilisation dans la préparation de catalyseurs. |
JP3819192B2 (ja) * | 1999-10-18 | 2006-09-06 | ダイヤニトリックス株式会社 | アクリロニトリルの製造法 |
US6585944B1 (en) * | 2000-10-17 | 2003-07-01 | Delphi Technologies, Inc. | Enhancement of the OSC properties of Ce-Zr based solid solutions |
JP4030740B2 (ja) * | 2001-10-11 | 2008-01-09 | ダイヤニトリックス株式会社 | アンモ酸化用触媒の製造方法 |
US20030186805A1 (en) * | 2002-03-28 | 2003-10-02 | Vanderspurt Thomas Henry | Ceria-based mixed-metal oxide structure, including method of making and use |
JP3874270B2 (ja) | 2002-09-13 | 2007-01-31 | トヨタ自動車株式会社 | 排ガス浄化フィルタ触媒及びその製造方法 |
JP2006043654A (ja) * | 2004-08-09 | 2006-02-16 | Toyota Motor Corp | 排ガス浄化触媒及びその製造方法 |
JP5063980B2 (ja) * | 2006-10-24 | 2012-10-31 | Dowaエレクトロニクス株式会社 | 排ガス浄化触媒用複合酸化物およびフィルター |
JP5190196B2 (ja) * | 2006-12-01 | 2013-04-24 | Dowaエレクトロニクス株式会社 | 排ガス浄化触媒用複合酸化物および排ガス浄化触媒、並びにディーゼル排ガス浄化用フィルター |
JP5528040B2 (ja) * | 2008-10-03 | 2014-06-25 | Dowaエレクトロニクス株式会社 | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ |
-
2009
- 2009-04-21 WO PCT/JP2009/057915 patent/WO2009131118A1/ja active Application Filing
- 2009-04-21 CN CN201510022932.0A patent/CN104759274A/zh active Pending
- 2009-04-21 US US12/935,701 patent/US8304364B2/en not_active Expired - Fee Related
- 2009-04-21 KR KR1020107025233A patent/KR101574553B1/ko not_active IP Right Cessation
- 2009-04-21 EP EP09735657.0A patent/EP2269730B1/en not_active Not-in-force
- 2009-04-21 CN CN2009801148889A patent/CN102015097A/zh active Pending
- 2009-04-22 JP JP2009104566A patent/JP4416830B2/ja not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06211525A (ja) | 1992-09-15 | 1994-08-02 | Rhone Poulenc Chim | 酸化第二セリウムをベースにした組成物、製法及び用途 |
JPH06315634A (ja) * | 1992-12-14 | 1994-11-15 | Sekiyu Sangyo Kasseika Center | 窒素酸化物接触還元用触媒構造体 |
JPH06279027A (ja) * | 1993-02-10 | 1994-10-04 | Rhone Poulenc Chim | ジルコニウム及びセリウムの混合酸化物を基とする組成物、その合成方法並びに使用方法 |
JP2003238159A (ja) | 2001-12-11 | 2003-08-27 | Kinya Adachi | 低温酸化還元能を有する複合酸化物とその製造方法 |
WO2005085137A1 (ja) * | 2004-03-08 | 2005-09-15 | Anan Kasei Co., Ltd. | 複合酸化物 |
JP2005281021A (ja) * | 2004-03-29 | 2005-10-13 | Nobuhito Imanaka | 希土類複合酸化物 |
JP2006224032A (ja) | 2005-02-18 | 2006-08-31 | Toyota Motor Corp | 排ガス浄化用触媒 |
Also Published As
Publication number | Publication date |
---|---|
EP2269730A4 (en) | 2014-07-09 |
KR101574553B1 (ko) | 2015-12-04 |
EP2269730B1 (en) | 2018-04-18 |
KR20110008083A (ko) | 2011-01-25 |
JP2009279581A (ja) | 2009-12-03 |
JP4416830B2 (ja) | 2010-02-17 |
US20110027135A1 (en) | 2011-02-03 |
EP2269730A1 (en) | 2011-01-05 |
CN102015097A (zh) | 2011-04-13 |
CN104759274A (zh) | 2015-07-08 |
US8304364B2 (en) | 2012-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5528040B2 (ja) | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ | |
WO2009131118A1 (ja) | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ | |
JP5190196B2 (ja) | 排ガス浄化触媒用複合酸化物および排ガス浄化触媒、並びにディーゼル排ガス浄化用フィルター | |
JP5063980B2 (ja) | 排ガス浄化触媒用複合酸化物およびフィルター | |
JP5574222B2 (ja) | Co酸化触媒及びそれを用いた排ガス浄化方法 | |
JP4768475B2 (ja) | Pm燃焼触媒用複合酸化物およびフィルター | |
JP2007216150A (ja) | 酸化触媒用複合酸化物およびフィルター | |
JP5427443B2 (ja) | 排ガス浄化触媒用複合酸化物および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ | |
EP3174634B1 (en) | Noble metal-free catalyst compositions | |
JP5973914B2 (ja) | 排ガス処理用触媒組成物の製造方法 | |
JP5345063B2 (ja) | セリウム含有複合酸化物およびその製造方法、pm燃焼用触媒、並びに、ディーゼルパティキュレートフィルタ | |
JP2009233642A (ja) | 排ガス浄化触媒用複合酸化物およびそれを用いた排ガス浄化用フィルタ | |
JP2009160556A (ja) | 排ガス浄化用触媒および排ガス浄化用触媒の製造方法 | |
JP2007229715A (ja) | 触媒担体及び触媒 | |
JP2010194437A (ja) | 排ガス浄化用触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980114888.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09735657 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009735657 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12935701 Country of ref document: US Ref document number: 6927/DELNP/2010 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107025233 Country of ref document: KR Kind code of ref document: A |