WO2020039903A1 - 排ガス浄化触媒用多孔質構造体及びそれを用いた排ガス浄化触媒並びに排ガス浄化方法 - Google Patents
排ガス浄化触媒用多孔質構造体及びそれを用いた排ガス浄化触媒並びに排ガス浄化方法 Download PDFInfo
- Publication number
- WO2020039903A1 WO2020039903A1 PCT/JP2019/030646 JP2019030646W WO2020039903A1 WO 2020039903 A1 WO2020039903 A1 WO 2020039903A1 JP 2019030646 W JP2019030646 W JP 2019030646W WO 2020039903 A1 WO2020039903 A1 WO 2020039903A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- less
- pore volume
- porous structure
- pore
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 238000000746 purification Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 21
- 239000011148 porous material Substances 0.000 claims abstract description 253
- 239000007789 gas Substances 0.000 claims abstract description 114
- 238000009826 distribution Methods 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 238000003860 storage Methods 0.000 claims abstract description 28
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims description 32
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 230000035515 penetration Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 76
- 239000000463 material Substances 0.000 description 56
- 239000000843 powder Substances 0.000 description 32
- 239000002002 slurry Substances 0.000 description 25
- 238000005259 measurement Methods 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- QTANTQQOYSUMLC-UHFFFAOYSA-O Ethidium cation Chemical compound C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 QTANTQQOYSUMLC-UHFFFAOYSA-O 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 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
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 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
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/66—Pore distribution
-
- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- 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
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0248—Coatings comprising impregnated particles
-
- 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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0864—Oxygen
-
- 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
- F01N3/24—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 characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
-
- 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
- F01N3/24—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 characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
-
- 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
- F01N3/24—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 characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- 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
- B01D2255/2063—Lanthanum
-
- 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
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/915—Catalyst supported on particulate filters
- B01D2255/9155—Wall flow filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9205—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9207—Specific surface
-
- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
-
- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/30—Honeycomb supports characterised by their structural details
- F01N2330/48—Honeycomb supports characterised by their structural details characterised by the number of flow passages, e.g. cell density
-
- 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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
-
- 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 a porous structure for an exhaust gas purifying catalyst, an exhaust gas purifying catalyst, and an exhaust gas purifying method.
- a three-way catalyst for purifying three components of carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxide (NO x ) in exhaust gas discharged from a gasoline engine, a diesel engine CO in the exhaust gas discharged from the oxidation catalyst for purifying HC (Diesel oxidation catalyst: DOC) and, NO x reduction catalyst for purifying NO x (Lean NO x Trap catalyst : LNT) , such as is discharged from the internal combustion engine
- Exhaust gas purifying catalysts for purifying exhaust gas have been proposed.
- the exhaust gas purifying catalyst generally has a configuration in which a catalyst layer in which a noble metal is supported on an inorganic material as a carrier is formed on a porous substrate having a honeycomb shape or the like.
- a porous material having a high specific surface area is usually used in order to increase the probability that the noble metal comes into contact with the exhaust gas component and improve the purification efficiency.
- Patent Documents 1 to 3 As described above, as a technique for increasing the probability that a noble metal comes into contact with an exhaust gas component and improving purification efficiency, those in which the pore volume in a catalyst layer is specifically designed are known (Patent Documents 1 to 3).
- an object of the present invention is to provide a porous structure for an exhaust gas purifying catalyst having excellent light-off performance, and an exhaust gas purifying catalyst and an exhaust gas purifying method using the same.
- the inventor has conducted intensive studies on the relationship between the pore volume distribution in the porous structure for an exhaust gas purifying catalyst and the light-off performance of the catalyst.
- the light-off performance can be effectively improved by setting the pore volume distribution of relatively fine pores having a pore diameter in the range of 5 to 25 nm, which has not been considered conventionally, in a specific range. I found what I could do.
- the present invention is based on the above findings, and is a porous structure for an exhaust gas purifying catalyst including an oxygen storage component and an inorganic porous material, wherein a pore diameter is 5 nm in a pore volume distribution measured by a mercury intrusion porosimeter.
- An object of the present invention is to provide a porous structure for an exhaust gas purifying catalyst, wherein a ratio of a pore volume of 15 nm or more and less than 25 nm to a pore volume of 15 nm or more and less than 15 nm is 1.3 or more and 2.5 or less.
- the “pore diameter” in the present invention refers to the pore diameter.
- the present invention is an exhaust gas purification catalyst having a substrate and a catalyst layer formed on the surface of the substrate, wherein the catalyst layer contains an oxygen storage component and an inorganic porous body,
- the exhaust gas purifying catalyst in a pore volume distribution measured by a mercury intrusion porosimeter, a ratio of a pore volume of 15 nm to less than 25 nm to a pore volume of 5 nm to less than 15 nm is 1.3 to 2.5.
- the present invention provides an exhaust gas purifying catalyst.
- the present invention also provides an exhaust gas purifying method for purifying exhaust gas by bringing exhaust gas discharged from an internal combustion engine into contact with an exhaust gas purifying catalyst.
- porous structure for an exhaust gas purifying catalyst of the present embodiment is, for example, the catalyst in an exhaust gas purifying catalyst having a base material and a catalyst layer formed on the surface of the base material. Used as a layer.
- the porous structure may be composed of a single catalyst layer, or may be composed of a plurality of catalyst layers.
- the porous structure for an exhaust gas purifying catalyst of the present embodiment preferably includes an oxygen storage component (also referred to as an OSC material; OSC is an abbreviation for oxygen storage capacity) and an inorganic porous material.
- an oxygen storage component also referred to as an OSC material; OSC is an abbreviation for oxygen storage capacity
- the porous structure of the porous structure for an exhaust gas purifying catalyst according to the present embodiment is mainly derived from an inorganic porous body, and further, when the oxygen storage component is a porous body, also derived from the oxygen storage component.
- the degree of porosity of the porous structure for an exhaust gas purifying catalyst is represented by a pore volume distribution measured by a mercury intrusion porosimeter, and is from 15 nm to 25 nm with respect to a pore volume (A) having a pore diameter of 5 nm to less than 15 nm. It is preferable that the ratio (B / A) of the pore volume (B) of less than the following specific range. That is, the value of B / A is preferably 1.3 or more and 2.5 or less, more preferably 1.4 or more and 2.3 or less, and particularly preferably 1.6 or more and 2.1 or less. preferable.
- the ratio of the pore volume (B) having a pore diameter of 15 nm to less than 25 nm (hereinafter, also referred to as “B / A ratio”) to the pore volume (A) having a pore diameter of 5 nm to less than 15 nm is 1.3 or more and 2.3.
- the reason why the light-off performance is improved by the porous structure of 5 or less is considered as follows. Exhaust gas easily flows into relatively large pores having a pore diameter of 15 nm or more and less than 25 nm. Therefore, by controlling the pore volume of the pores to have a specific ratio, the exhaust gas is reduced in the fine pores in the porous structure.
- the amount flowing into the pores can be controlled, and the contact between the catalytically active component present in the pores and the exhaust gas can be increased.
- the specific surface area is increased. Therefore, by controlling the pore volume of the pores to have a specific ratio, the exhaust gas is reduced to a catalytically active component. An effective area for contacting the surface can be secured.
- the porous Exhaust gas can efficiently contact the catalytically active components arranged in the structure, and the light-off performance can be improved.
- the pore volume (A) of the pores having a pore diameter of 5 nm or more and less than 15 nm and the pore volume (B) of the pores having a pore diameter of 15 nm or more and less than 25 nm in the porous structure is important in the present invention.
- the present inventor believes that the light-off performance can be improved by setting the B / A ratio in a specific range regardless of the arrangement of these pores in the thickness direction.
- the pore volume having a pore diameter of 5 nm or more and less than 25 nm is preferably 600 ⁇ 10 ⁇ 3 cm 3 / g or less, and particularly preferably 10 ⁇ 10 ⁇ 3 cm 3. / G or more and 350 ⁇ 10 ⁇ 3 cm 3 / g or less.
- the pore volume distribution is measured by a mercury intrusion porosimeter.
- the measurement using a mercury intrusion porosimeter is a method of measuring the distribution of pores (voids) by changing the pressure applied to mercury and measuring the amount of mercury that has penetrated the pores at that time.
- the pore volume distribution can be obtained by measuring the pressure P and the amount V of liquid entering at that time while changing the pressure P, and converting the pressure P into the pore diameter D from the above formula to obtain a DV curve.
- the pore volume can be obtained by measuring the amount of mercury that has entered the pores.
- the porous structure is a catalyst layer formed on the substrate surface of the exhaust gas purifying catalyst
- the pore diameter of the substrate is usually 500 nm or more
- the presence or absence of the substrate is determined by the pore volume distribution having a pore diameter of 25 nm or less.
- the pore volume distribution measured by the mercury intrusion porosimeter may be measured in a state of an exhaust gas purifying catalyst having a porous structure and a substrate.
- the pore volume distribution can be measured by the method described in Examples described later.
- the porous structure of the present embodiment in the pore volume distribution measured by a mercury intrusion porosimeter, the porous structure has at least one peak top in a range of a pore diameter of 15 nm or more and less than 25 nm.
- the exhaust gas can be efficiently penetrated, and the contact between the catalytically active component and the exhaust gas is enhanced to further improve the light-off performance.
- the peak may be present in another range.
- ⁇ The“ peak top ” here is calculated as follows. That is, the pore volume is measured by a mercury intrusion porosimeter in the range of the pore diameter of 15 nm or more and less than 25 nm. In the DV curve obtained, the increase in pore volume is calculated for two adjacent measurement points. Next, a measurement section where the increase in the pore volume is the largest is extracted, and the pore diameter on the smaller side of the section is defined as the peak top. The measuring points are based on the specifications of the measuring device shown in the examples.
- the pore volume in the range of the pore diameter of 5 nm or more and less than 15 nm is preferably 250 ⁇ 10 ⁇ 3 cm 3 / g or less, particularly 5 ⁇ , from the viewpoint of further improving the light-off performance. It is more preferably from 10 ⁇ 3 cm 3 / g to 150 ⁇ 10 ⁇ 3 cm 3 / g.
- the pore volume in the range of the pore diameter of 15 nm or more and less than 25 nm is preferably 400 ⁇ 10 ⁇ 3 cm 3 / g or less, particularly 5 ⁇ 10 ⁇ 3 cm 3 / g or more and 250 ⁇ 10 ⁇ 3 from the same viewpoint. cm 3 / g or less is more preferable.
- the pore diameter of the inorganic porous material powder and / or the oxygen storage component powder constituting the catalyst layer, and the inorganic porous material powder and the oxygen storage component powder And the firing temperature and time may be adjusted.
- the pore volume distribution in the porous structure of the present embodiment is not limited to other configurations in the pore volume distribution as long as the B / A ratio in the range of the pore diameter of 5 nm or more and less than 25 nm is within the above range.
- Preferable examples of the pore volume distribution measured including the substrate include those having the following pore volume ratios.
- the proportion of the pore volume having a pore diameter of 5 nm or more and less than 15 nm is preferably 5% or more and 35% or less, more preferably 5% or more and 20% or less.
- the proportion of the pore volume having a pore diameter of 15 nm or more and less than 25 nm in the total pore volume is preferably 10% or more and 50% or less, and more preferably 13% or more and 30% or less.
- total pore volume refers to a pore volume in a range of 3 nm to 350,000 nm measured by a mercury intrusion porosimeter, and refers to not only pores derived from a porous structure but also a substrate. It also includes the volume of the pores.
- the pore volume distribution of the porous structure measured for each substrate since the pore diameter of the pores of the substrate is usually 500 nm or more, regardless of the presence or absence of the substrate, the pore diameter in the region of less than 500 nm The pore volume distribution can be determined.
- the exhaust gas purifying catalyst of the present invention is provided with the porous structure of the present invention on the base material, the pore volume distribution of the porous structure of the present invention measured for each of the base materials described above. Corresponds to the pore volume distribution of the exhaust gas purifying catalyst in the present invention. Examples of the substrate will be described later.
- the volume ratio is preferably 15% or more and 40% or less, more preferably 15% or more and 35% or less, and even more preferably 15% or more and 30% or less.
- the pores whose pore diameters are observed in the range of 5 nm or more and 200 nm or less are mainly derived from the porous structure. Therefore, in this measurement, there is essentially no difference in the result between the case where the porous structure itself is the object of measurement and the case where the substrate having the porous structure is the object of measurement.
- the ratio of the pore volume of the pores having a pore diameter of 15 nm to less than 25 nm to the pore volume of the pores having a pore diameter of 5 nm to 200 nm is 20% to 60%. Or less, more preferably 25% or more and 55% or less, and even more preferably 30% or more and 50% or less.
- the porous structure preferably contains a catalytically active component.
- a catalytically active component platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os), silver (Ag), copper (Cu), iron (Fe) , Manganese (Mn) and cobalt (Co), and at least one selected from platinum (Pt), palladium (Pd) and rhodium (Rh). It is preferable to use it from the viewpoint of improving exhaust gas purification performance.
- the porous structure has a structure of two or more layers including a lower catalyst layer and an upper catalyst layer
- the inclusion of different catalytic active components in the lower catalyst layer and the upper catalyst layer enhances the exhaust gas purification performance.
- the lower catalyst layer is a layer located on the substrate side when the porous structure is formed on the substrate surface, and the upper catalyst layer is opposite to the substrate with respect to the lower catalyst layer. It is a layer located on the side.
- the porous structure may have another layer in addition to the lower catalyst layer and the upper catalyst layer, for example, may have another layer between the substrate and the lower catalyst layer, Another layer may be provided between the lower catalyst layer and the upper catalyst layer.
- the catalytically active component is preferably supported in a porous structure, and specifically, is preferably supported on an oxygen storage component and an inorganic porous material constituting the porous structure.
- “supported” refers to a state of being physically or chemically adsorbed or held on the outer surface or the inner surface of the pore.
- one particle carries another particle, for example, by measuring the particle size when observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the average particle diameter of particles existing on the surface of one particle is preferably 10% or less, more preferably 3% or less, with respect to the average particle diameter of the one particle. It is particularly preferred that it is 1% or less.
- the average particle diameter here is an average value of the maximum Feret diameter of 30 or more particles observed by SEM.
- the maximum Feret diameter is the maximum distance of a particle pattern between two parallel lines.
- the amount of the catalytically active component contained in the porous structure is preferably 0.1% by mass or more and 10% by mass or less in the porous structure from the viewpoint of further increasing the light-off performance while reducing the cost. More preferably, it is 0.15% by mass or more and 7% by mass or less.
- the content of the catalytically active component in the porous structure is measured, for example, by the following method. First, the porous structure is dissolved to form a solution, and the amount of each element is measured by ICP-AES using the solution as a measurement object.
- the amount of the catalytically active component was determined, and the ratio of the amount of the catalytically active component in terms of the element when the amount of the remaining elements was converted to their oxides and the total amount was taken as 100. calculate.
- the porous structure is formed on the base material, the porous structure is separated from the base material, and the same measurement is performed on the separated porous structure.
- the porous structure has an oxygen storage component and an inorganic porous body.
- the OSC material for example, ceria (CeO 2) and ceria - zirconia composite oxide (hereinafter, CeO 2 -ZrO described 2 both) are exemplified, it is preferred for the high OSC ability is CeO 2 -ZrO 2 .
- CeO 2 -ZrO 2 is a solid solution of CeO 2 and ZrO 2 .
- the solid solution of CeO 2 and ZrO 2 can be confirmed by using an X-ray diffractometer (XRD) based on whether or not a diffraction pattern derived from CeO 2 -ZrO 2 is obtained.
- XRD X-ray diffractometer
- the porous structure contains an inorganic porous material in addition to the oxygen storage component (OSC material).
- OSC material itself is also a porous material, supporting a catalytically active component. It is preferable because it is easy.
- the fact that the OSC material is a porous material in the porous structure means that the porous structure is observed by a scanning electron microscope and the composition of the porous structure is analyzed by energy dispersive X-ray spectroscopy (EDX). Or by analyzing with an electron probe microanalyzer (EPMA).
- EDX energy dispersive X-ray spectroscopy
- EPMA electron probe microanalyzer
- Oxygen storage components such as CeO 2 and CeO 2 —ZrO 2 are added with rare earth elements other than cerium, alkaline earth metal elements such as Ba, Sr, and Ca, and elements such as magnesium (Mg) and aluminum (Al). You may.
- addition includes “solid solution” and “modification”.
- Modification refers to a state in which another element is present on the surface of the oxygen storage component, and is a concept that includes “support”.
- the “surface” here refers to the inner surface of the pores of the oxygen storage component or the outer surface of the oxygen storage component.
- rare earth elements other than cerium, scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium ( Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
- These rare earth elements are added to the oxygen storage component, for example, as oxides. These may be two or more composite oxides.
- These oxides of rare earth elements other than cerium may or may not form a solid solution with CeO 2 or CeO 2 —ZrO 2 . Whether or not an oxide of a rare earth element other than cerium forms a solid solution with CeO 2 or CeO 2 -ZrO 2 can be confirmed by an X-ray diffractometer (XRD) in the same manner as described above.
- XRD X-ray diffractometer
- Examples of the inorganic porous body used together with the oxygen storage component include a porous body made of an inorganic compound other than the oxygen storage component.
- Examples of the inorganic porous material include rare earth oxides (Re 2 O 3 ) such as Al 2 O 3 (alumina), ZrO 2 , SiO 2 , TiO 2 and La 2 O 3 , zeolite (aluminosilicate), and apatite-type lanthanum.
- Examples of the alumina include alumina of each crystal type of ⁇ , ⁇ , ⁇ , and ⁇ .
- examples thereof include Al, Zr, Si, Ti, rare earth elements, phosphates such as Mg and Zn, silicates and borates, and sparingly soluble sulfates of alkaline earth metals such as Ba and Sr.
- the inorganic porous material is an apatite type lanthanum silicate, the presence or absence of such an inorganic porous material can be confirmed by X-ray diffraction measurement and composition analysis by ICP-AES.
- an inorganic porous material other than the OSC material in the porous structure can be confirmed by observing the porous structure with a scanning electron microscope and determining the composition of the porous structure by energy dispersive X-ray spectroscopy ( It can be confirmed by analyzing with EDX) or analyzing with an electron probe microanalyzer (EPMA). Further, when a binder is used in the porous structure as described later, the binder component and the inorganic porous material or the OSC material may be the same material.
- the inorganic porous body such as alumina.
- Other materials include lanthanum oxide, ZrO 2 , CeO 2, and the like.
- “addition” includes “solid solution” and “modification” as described for the oxygen storage component.
- CeO 2 is an oxygen storage component
- the “inorganic porous body other than the oxygen storage component” includes those that modify or carry an oxygen storage component such as CeO 2 . Therefore, the “inorganic porous body other than the oxygen storage component” may be one in which CeO 2 is modified on the inner surface or outer surface of a pore such as alumina.
- the porous structure may have a single-layer structure or a multi-layer structure.
- each layer has both an OSC material and an inorganic porous body.
- one layer may have one of the OSC material and the inorganic porous body, and the other layer may have the other.
- the porous structure of the present embodiment has a two-layer structure of an upper catalyst layer and a lower catalyst layer, and each layer having an OSC material and an inorganic porous material further enhances exhaust gas purification performance. It is preferred in that respect.
- the porous structure has a structure of two or more layers, and each layer has an OSC material and an inorganic porous body
- a method for distinguishing each layer for example, the type and amount of the catalytically active component contained in each layer are different. If they are different, there is a method of distinguishing them according to the difference. For example, it is possible to discriminate a sample in which the catalyst is cut in a cross section orthogonal to the longitudinal direction and embedded in a resin based on a fluctuation curve obtained by quantifying the distribution of the catalytically active component by EDX line analysis.
- the content of the OSC material in the porous structure should be 5% by mass or more and 80% by mass or less from the viewpoint of achieving a balance between heat resistance and enhancing exhaust gas purification performance at low temperatures by exhibiting OSC performance. Is preferably 10% by mass or more and 60% by mass or less.
- the content of the inorganic porous material in the porous structure is preferably from 5% by mass to 80% by mass, and more preferably from 10% by mass to 60% by mass, from the same viewpoint as described above. preferable.
- the content of the OSC material is larger than the content of the inorganic porous material, so that the fluctuation of the air-fuel ratio (A / F) of the exhaust gas flowing into the exhaust gas purification catalyst can be sufficiently absorbed from a low temperature.
- the ratio of the content of the inorganic porous material to the content of the OSC material is preferably 0.2 or more and 0.8 or less, and 0.3 or more and 0.7 or less. It is more preferable that it is not more than 0.4, and it is more preferable that it is 0.4 or more and 0.6 or less.
- the content of the OSC material may be larger than the content of the inorganic porous material when viewed as the entire porous structure. It is preferable that the above ratio be satisfied when viewed, more preferably the content of the OSC material in each layer is larger than the content of the inorganic porous material, and further preferably each layer satisfies the above ratio.
- the contents of the OSC material and the inorganic porous material in the porous structure are measured by, for example, the following method.
- the OSC material is, for example, CeO 2 -ZrO 2
- the inorganic porous body is, for example, Al 2 O 3
- the porous structure is dissolved to form a solution, and the solution is used as a measurement target to determine each element. Is measured by ICP-AES.
- the amounts of CeO 2 , ZrO 2 , and Al 2 O 3 were determined, and the amounts of the remaining elements were converted to their oxides, and the total amount was set to 100, in terms of oxide.
- the ratio of the amounts of CeO 2 , ZrO 2 and Al 2 O 3 is calculated.
- the amount of the OSC material other than CeO 2 -ZrO 2 and the amount of the inorganic porous material other than Al 2 O 3 are determined in the same manner.
- the porous structure is formed on the substrate, the porous structure is separated from the substrate, and the measurement is similarly performed on the separated porous structure.
- the porous structure of the present embodiment by using this as an exhaust gas purification catalyst formed as a catalyst layer on the surface of the base material, can efficiently contact the exhaust gas with the catalytically active component even at the time of starting operation. Light-off performance.
- a porous substrate is preferably used, and the shape thereof is, for example, a honeycomb shape.
- the material of the base material for example, alumina (Al 2 O 3 ), mullite (3Al 2 O 3 -2SiO 2 ), cordierite (2MgO-2Al 2 O 3 -5SiO 2 ), aluminum titanate (Al 2 TiO 5) ) And silicon carbide (SiC).
- a slurry containing an OSC material powder and an inorganic porous material powder and, if necessary, a salt or a binder of a catalytically active component is used. After preparing and applying (for example, wash-coating) to a substrate, drying and baking to form a catalyst layer as a porous structure on the surface of the substrate.
- the porous material of the present invention having a desired B / A ratio can be obtained.
- the porous structure and the exhaust gas purifying catalyst can be easily obtained.
- the term “pore diameter” as used herein means the peak of the largest differential pore volume when measured in the range of 3 nm to 500 nm so that the pore volume of the inorganic porous material and the primary particles and secondary particles of the OSC material can be confirmed. Is the pore diameter.
- the thickness is preferably 3 to 50 nm, more preferably 3 to 35 nm, and particularly preferably 5 to 25 nm.
- the OSC material preferably has a pore diameter of 3 to 50 nm, more preferably 5 to 50 nm, and more preferably 10 to 50 nm. More preferably, it is even more preferably from 15 to 45 nm.
- BET specific surface area is preferably 30m 2 / g ⁇ 300m 2 / g, particularly preferably 50 m 2 / g ⁇ Those having a capacity of 200 m 2 / g are suitably used from the viewpoint of the catalytic active component carrying properties and exhaust gas purification performance.
- OSC material if it is a porous body, a porous structure regardless of whether a multilayer or a single layer, BET specific surface area is preferably 10m 2 / g ⁇ 200m 2 / g Particularly preferably, those having a range of 30 m 2 / g to 150 m 2 / g are suitably used from the viewpoints of the catalytic active component supportability and exhaust gas purification performance.
- the inorganic porous body may be subjected to laser diffraction regardless of whether the porous structure is a single layer or a multilayer.
- the volume cumulative particle diameter D 50 at a cumulative volume of 50% by volume according to the scattering type particle size distribution measurement method is preferably 3 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 45 ⁇ m, and still more preferably 5 ⁇ m to 40 ⁇ m.
- the volume cumulative particle diameter D 50 is preferably 3 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and still more preferably 5 ⁇ m to 10 ⁇ m.
- ⁇ Water is used as a liquid medium of the slurry.
- the salt of the catalytically active component include palladium nitrate, rhodium nitrate, platinum nitrate and the like.
- the temperature at which the substrate coated with the slurry is fired is preferably 400 ° C to 800 ° C in air, more preferably 450 ° C to 600 ° C.
- the firing time is preferably 30 minutes to 6 hours, more preferably 1 hour to 4 hours.
- the slurry applied to the substrate is preferably dried in the air before firing, and the temperature is preferably from 40 ° C to 200 ° C, more preferably from 70 ° C to 150 ° C.
- the drying time is preferably 5 minutes to 6 hours, more preferably 10 minutes to 2 hours.
- the porous structure for an exhaust gas purifying catalyst and the exhaust gas purifying catalyst of the present invention produced in the above steps have excellent light-off performance.
- the exhaust gas purifying catalyst for the porous structure and the catalyst of the present invention by contacted with exhaust gas discharged from an internal combustion engine, an efficient NO x, HC, the purification of CO possible.
- the exhaust gas purifying catalyst of the present invention by using the internal combustion engine, NO x in the exhaust gas during operation startup, HC, CO can efficiently purify.
- Example 1 (1) Preparation of slurry for lower catalyst layer An aqueous solution of palladium nitrate was placed in a container, and an OSC material powder (CeO 2 -ZrO 2 composite oxide (CeO 2 : 40% by mass, ZrO 2 : 50% by mass, other 10% by mass contained) ), BET specific surface area: 85m 2 / g, pore size: 20nm, D 50: 6 ⁇ m) , first inorganic porous material powder (4% by weight of La 2 O 3 Al 2 O 3 modified with, BET specific surface area : 150m 2 / g, pore size: 17.6nm, D 50: 35 ⁇ m) , and, Al 2 O 3 modified with a second inorganic porous material powder (4% by weight of La 2 O 3, BET specific surface area: 170 m 2 / g, pore size: 9.8 nm, D 50 : 30 ⁇ m) and stirred.
- OSC material powder CeO 2 -ZrO 2 composite oxide
- the mass ratio of the first inorganic porous body powder to the second inorganic porous body powder was 91: 9.
- alumina sol D 50 : ⁇ 0.2 ⁇ m
- the OSC material was 60% by mass
- alumina derived from alumina sol 8% by mass and palladium 3% by mass.
- the slurry for the upper catalyst layer was prepared as follows: 60% by mass of an OSC material, 31% by mass of an inorganic porous material, 8% by mass of alumina derived from alumina sol, It is prepared so as to ethidium 1 wt% of the composition ratio formed by.
- Example 2 In preparing the slurry for the lower catalyst layer in (1) of Example 1, the mass ratio of the first inorganic porous material powder and the second inorganic porous material powder was changed to 50:50. Except that point, an exhaust gas purifying catalyst of Example 2 was obtained in the same manner as Example 1.
- Example 3 When preparing the slurry for the lower catalyst layer in (1) of Example 1, the inorganic porous material powder (La 2 O 3 is 1) is used instead of the first inorganic porous material powder and the second inorganic porous material powder. (% By mass modified Al 2 O 3 , BET specific surface area: 150 m 2 / g, pore diameter: 16.0 nm, D 50 : 35 ⁇ m) were used. Except that point, an exhaust gas purifying catalyst of Example 3 was obtained in the same manner as Example 1.
- Example 4 In preparing the slurry for the lower catalyst layer in (1) of Example 1, the mass ratio of the first inorganic porous material powder and the second inorganic porous material powder was changed to 30:70. Except that point, an exhaust gas purifying catalyst of Example 4 was obtained in the same manner as Example 1.
- Example 5 In preparing the slurry for the lower catalyst layer in (1) of Example 1, the mass ratio of the first inorganic porous material powder and the second inorganic porous material powder was changed to 9:91. Except that point, an exhaust gas purifying catalyst of Example 5 was obtained in the same manner as Example 1.
- Example 6 Preparation of slurry for lower catalyst layer
- the mass ratio of the first inorganic porous material powder and the second inorganic porous material powder was set to 100: Changed to 0. Except for that point, a slurry for a lower catalyst layer was prepared in the same manner as in Example 1.
- the slurry was further stirred to prepare a slurry for the upper catalyst layer, which was 60% by mass of the OSC material, 31% by mass of the third inorganic porous material, and 8% by mass of alumina derived from alumina sol when the slurry was used as the catalyst layer. , It made be prepared as a rhodium 1 wt% of the composition ratio.
- the pore volume distribution of the exhaust gas purifying catalyst was measured by the following method, and the following items were obtained. Table 1 shows the results. 1) Pore volume A (cm 3 / g) of pores having a pore diameter of 5 nm or more and less than 15 nm 2) Ratio of A to total pore volume (%) 3) Ratio (%) of pore volume A of pores having a pore diameter of 5 nm to less than 15 nm to pore volume of pores having a pore diameter of 5 nm to 200 nm.
- Pore volume B (cm 3 / g) of pores having a pore diameter of 15 nm or more and less than 25 nm 5) Ratio of B to total pore volume (%) 6) Ratio (%) of pore volume B of pores having a pore diameter of 15 nm to less than 25 nm to pore volume of pores having a pore diameter of 5 nm to 200 nm. 7) B / A ratio 8) Presence / absence of peak top of pore diameter in the range of 15 nm or more and less than 25 nm (if there is a peak top, measured value (nm) is shown)
- Purification rate (%) (XY) / X ⁇ 100
- the inlet gas temperature of the catalyst when the purification rate reached 50% was determined as the light-off temperature T50. T50 was measured at the time of temperature rise.
- the porous structure for exhaust gas purifying catalysts excellent in light-off performance and an exhaust gas purifying catalyst using the same are provided.
- the exhaust gas purifying method of the present invention can efficiently purify NO x , HC, and CO in exhaust gas discharged from an internal combustion engine at the time of starting operation by using the exhaust gas purifying catalyst of the present invention.
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)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Toxicology (AREA)
- Ceramic Engineering (AREA)
- Emergency Medicine (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Nanotechnology (AREA)
Abstract
Description
排ガス浄化触媒は、通常、ハニカム形状等の多孔質基材上に、担体である無機材料に貴金属が担持された触媒層が形成された構成を有している。この無機材料は通常、貴金属が排ガス成分に接触する確率を高めて浄化効率を向上させるため、比表面積の高い多孔質なものが用いられている。
これに対し、特許文献1~3に記載された従来の排ガス浄化触媒に関しては、触媒層の細孔容積に着目した技術であってもライトオフ性能が十分とは言い難かった。
前記排ガス浄化触媒は、水銀圧入ポロシメータにより測定される細孔容積分布において、細孔径が5nm以上15nm未満の細孔容積に対する15nm以上25nm未満の細孔容積の比が1.3以上2.5以下である、排ガス浄化触媒を提供するものである。
排ガス浄化触媒用多孔質構造体の多孔質の程度は、これを水銀圧入ポロシメータにより測定される細孔容積分布で表すと、細孔径が5nm以上15nm未満の細孔容積(A)に対する15nm以上25nm未満の細孔容積(B)の比(B/A)が以下の特定の範囲であることが好ましい。すなわち、B/Aの値が1.3以上2.5以下であることが好ましく、1.4以上2.3以下であることがより好ましく、1.6以上2.1以下であることが特に好ましい。
上述した通り、本発明において重要なのは、多孔質構造体中の細孔径が5nm以上15nm未満の細孔の細孔容積(A)と細孔径が15nm以上25nm未満の細孔の細孔容積(B)とのバランスであるから、厚み方向におけるこれらの細孔の配置に関わらず、B/A比が特定範囲であることでライトオフ性能を向上させることができると本発明者は考えている。
一方、全細孔容積中、細孔径15nm以上25nm未満の細孔容積の割合は、10%以上50%以下であることが好ましく、13%以上30%以下であることがより好ましい。なお、本発明でいう「全細孔容積」とは、水銀圧入ポロシメータにより測定される3nm~350000nmの範囲における細孔容積をいい、多孔質構造体に由来する細孔のみならず、基材の細孔の容積も含むものである。
なお、基材ごと測定した多孔質構造体の細孔容積分布において、基材の細孔の細孔径は通常500nm以上であることから、基材の有無に関わらず細孔径500nm未満の領域にて細孔容積分布を求めることができる。
なお、上述した通り、本発明の排ガス浄化触媒は、基材に本発明の多孔質構造体を設けたものであるから、上記基材ごと測定した本発明の多孔質構造体の細孔容積分布は、本発明における排ガス浄化触媒の細孔容積分布に該当する。基材の例は後述する。
例えば、多孔質構造体を下層触媒層及び上層触媒層を含む二層以上の構成とする場合には、下層触媒層及び上層触媒層に異なる触媒活性成分を含有させることが、排ガス浄化性能を高める点で好ましく、特に下層触媒層にパラジウム(Pd)を含有させ、上層触媒層に白金(Pt)又はロジウム(Rh)を含有させることが、排ガス浄化性能を一層高める点で好ましい。
本実施形態では、多孔質構造体は酸素貯蔵成分(OSC材料)に加えて無機多孔質体を含有するものであるが、OSC材料それ自体も多孔質体であることが触媒活性成分を担持しやすいため好ましい。多孔質構造体においてOSC材料が多孔質体であることは、走査型電子顕微鏡により多孔質構造体を観察すると共に、多孔質構造体の組成をエネルギー分散型X線分光法(EDX)にて分析したり、電子プローブマイクロアナライザ(EPMA)にて分析することで確認できる。
なお、無機多孔質体がアパタイト型ランタンシリケートである場合、かかる無機多孔質体の有無はX線回折測定及びICP-AESによる組成分析により確認できる。また、多孔質構造体においてOSC材料以外の無機多孔質体が存在することは、走査型電子顕微鏡により多孔質構造体を観察し、且つ多孔質構造体の組成をエネルギー分散型X線分光法(EDX)にて分析したり、電子プローブマイクロアナライザ(EPMA)にて分析することで確認できる。
また、後述するように多孔質構造体中にバインダーを用いた場合、バインダー成分と、無機多孔質体やOSC材料とが同じ材料となることがある。この場合に関しても、バインダー成分と、無機多孔質体やOSC材料とを区別する方法として、上述のようにEDXやEPMAを用い、材料の粒径や各材料に添加される成分等を分析することが挙げられる。
(1)下層触媒層用スラリーの調製
容器に硝酸パラジウム水溶液を入れ、OSC材料粉末(CeO2-ZrO2複合酸化物(CeO2:40質量%、ZrO2:50質量%、その他10質量%含有)、BET比表面積:85m2/g、細孔径:20nm、D50:6μm)、第一無機多孔質体粉末(4質量%のLa2O3で修飾されたAl2O3、BET比表面積:150m2/g、細孔径:17.6nm、D50:35μm)、及び、第二無機多孔質体粉末(4質量%のLa2O3で修飾されたAl2O3、BET比表面積:170m2/g、細孔径:9.8nm、D50:30μm)を入れて撹拌した。第一無機多孔質体粉末と第二無機多孔質体粉末との質量比が91:9となるように調製した。次いで、上述した粉末材料が十分に拡散した後に、バインダーとしてアルミナゾル(D50:<0.2μm)を入れ、更に撹拌して、下層触媒層用スラリーを調製した。スラリーは、触媒層とした際にOSC材料60質量%、無機多孔質体(第一無機多孔質体+第二無機多孔質体)29質量%、アルミナゾル由来のアルミナ8質量%、パラジウム3質量%の構成比率となるように調製されてなる。
容器に硝酸ロジウム水溶液を入れ、OSC材料粉末(CeO2-ZrO2複合酸化物(CeO2:15質量%、ZrO2:70質量%、その他15質量%含有、BET比表面積:55m2/g、細孔径:40nm、D50:6μm)及び無機多孔質体粉末(4質量%のLa2O3で修飾されたAl2O3、BET比表面積:150m2/g、細孔径:14.0nm、D50:7μm)を入れて撹拌した。次いで、上述した粉末材料が十分に拡散した後にバインダーとしてアルミナゾル(D50:<0.2μm)を入れ、更に撹拌して、上層触媒層用スラリーを調製した。スラリーは、触媒層とした際にOSC材料60質量%、無機多孔質体31質量%、アルミナゾル由来のアルミナ8質量%、ロジウム1質量%の構成比率となるように調製されてなる。
セラミックス製ハニカム基材(セル数600cpi、壁厚3.5mil)に、(1)で調製した下層触媒層用スラリーをコートし、150℃で1時間乾燥させた後、450℃で3時間焼成して、コート量が95g/Lの下層触媒層を形成した。次いで、下層触媒層上に(2)で調製した上層触媒層用スラリーをコートし、150℃で1時間乾燥させた後、450℃で3時間焼成して、コート量が50g/Lの上層触媒層を形成し、基材上に2層の触媒層(多孔質構造体)が形成された排ガス浄化触媒を作製した。
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末の質量比を50:50に変更した。その点以外は、実施例1と同様にして、実施例2の排ガス浄化触媒を得た。
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末に替えて、無機多孔質体粉末(La2O3が1質量%修飾されたAl2O3、BET比表面積:150m2/g、細孔径:16.0nm、D50:35μm)を用いた。その点以外は実施例1と同様にして、実施例3の排ガス浄化触媒を得た。
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末の質量比を30:70に変更した。その点以外は、実施例1と同様にして、実施例4の排ガス浄化触媒を得た。
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末の質量比を9:91に変更した。その点以外は、実施例1と同様にして、実施例5の排ガス浄化触媒を得た。
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末の質量比を0:100に変更した。その点以外は、実施例1と同様にして、比較例1の排ガス浄化触媒を得た。
(1)下層触媒層用スラリーの調製
実施例1の(1)の下層触媒層用スラリーの調製の際に、第一無機多孔質体粉末及び第二無機多孔質体粉末の質量比を100:0に変更した。その点以外は、実施例1と同様にして、下層触媒層用スラリーを調製した。
容器に硝酸ロジウム水溶液を入れ、OSC材料粉末(CeO2-ZrO2複合酸化物(CeO2:15質量%、ZrO2:70質量%、その他15質量%含有、BET比表面積:55m2/g、細孔径:40nm、D50:6μm)、第三無機多孔質体粉末(4質量%のLa2O3で修飾されたAl2O3、BET比表面積:150m2/g、細孔径:9.8nm、D50:7μm)を入れて撹拌した。次いで、上述した粉末材料が十分に拡散した後にバインダーとしてアルミナゾル(D50:<0.2μm)を入れ、更に撹拌して、上層触媒層用スラリーを調製した。スラリーは、触媒層とした際にOSC材料60質量%、第三無機多孔質体31質量%、アルミナゾル由来のアルミナ8質量%、ロジウム1質量%の構成比率となるように調製されてなる。
セラミックス製ハニカム基材(セル数600cpi、壁厚3.5mil)に、実施例6の(1)で調製した下層触媒層用スラリーをコートし、150℃で1時間乾燥させた後、450℃で3時間焼成して、コート量が95g/Lの下層触媒層を形成した。次いで、下層触媒層上に、実施例6の(2)で調製した上層触媒層用スラリーをコートし、150℃で1時間乾燥させた後、450℃で3時間焼成して、コート量が50g/Lの上層触媒層を形成し、排ガス浄化触媒を作製した。
1)細孔径5nm以上15nm未満の細孔の細孔容積A(cm3/g)
2)全細孔容積に対するAの割合(%)
3)細孔径が5nm以上200nm以下の細孔の細孔容積に対する細孔径が5nm以上15nm未満の細孔の細孔容積Aの割合(%)
4)細孔径15nm以上25nm未満の細孔の細孔容積B(cm3/g)
5)全細孔容積に対するBの割合(%)
6)細孔径が5nm以上200nm以下の細孔の細孔容積に対する細孔径が15nm以上25nm未満の細孔の細孔容積Bの割合(%)
7)B/A比
8)細孔径15nm以上25nm未満の範囲における細孔径ピークトップの有無(ピークトップがある場合にはその測定値(nm)を示す)
測定装置としては、株式会社島津製作所製自動ポロシメータ「オートポアIV9520」を用いて、下記条件・手順で測定を行った。
(測定条件)
測定環境:25℃
測定セル:試料室体積 3cm3、圧入体積 0.39cm3
測定範囲:0.0035MPa から 254.925MPa まで
測定点:131点(隣り合う測定点の細孔径をD1、D2(D1>D2)としたとき、各細孔径の常用対数の差:logD1-logD2=0.037となるように測定圧力を決定した)
圧入体積:25%以上80%以下になるように調節した。
(低圧パラメーター)
排気圧力:50μmHg
排気時間:5.0min
水銀注入圧力:0.0034MPa
平衡時間:10sec
(高圧パラメーター)
平衡時間:10sec
(水銀パラメーター)
前進接触角:130.0degrees
後退接触角:130.0degrees
表面張力:485.0mN/m(485.0dyne/cm)
水銀密度:13.5335g/mL
(測定手順)
(1)実施例・比較例で得た排ガス浄化触媒において基材に2層の触媒層が形成された基材外壁部を除く部分を10mm×10mm×10mmで切り出してサンプルとし、測定を行った。
(2)低圧部で0.0035MPaから0.2058MPa以下の範囲で46点測定。
(3)高圧部で0.2241MPaから254.9250MPa以下の範囲で85点測定。
(4)水銀注入圧力及び水銀注入量から、細孔径分布を算出する。
なお、前記(2)、(3)、(4)は、装置付属のソフトウエアにて、自動で行った。その他の条件はJIS R 1655:2003に準じた。
(T50測定条件)
排ガス浄化触媒(触媒容積15ml)に、A/Fが14.6である下記組成モデルガスをA/Fが14.4~14.8の範囲で変動するようにCO濃度とO2濃度を調整しつつ、25L/minで流通させた。排ガス浄化触媒に流入するガス温度を常温から所定昇温速度で漸次上昇させていき、触媒を通過した排ガスに含まれるHC、NOx、CO量を下記装置にて求め、X:触媒未設置のときの検出量、Y:触媒設置後の検出量としたときに、下記式にて浄化率を求めた。
浄化率(%)=(X-Y)/X×100
浄化率が50%に達したときの触媒の入口ガス温度をライトオフ温度T50として求めた。T50は、昇温時について測定した。
・モデルガス(組成は体積基準):CO:0.5%、C3H6:1200ppmC、NO:500ppm、O2:0.50%、CO2:14%、H2O:10%、H2:0.17%、N2:残部
・昇温速度:20℃/分
・HC、NOx、CO量の測定:評価装置として堀場製作所社製MOTOR EXHAUST GAS ANALYZER MEXA7100を用いて行った。
Claims (10)
- 酸素貯蔵成分及び無機多孔質体を含む排ガス浄化触媒用多孔質構造体であって、
水銀圧入ポロシメータにより測定される細孔容積分布において、細孔径が5nm以上15nm未満の細孔容積に対する15nm以上25nm未満の細孔容積の比が1.3以上2.5以下である、排ガス浄化触媒用多孔質構造体。 - 前記細孔容積分布において、細孔径が15nm以上25nm未満の範囲内に少なくとも1つのピークトップを有する、請求項1に記載の排ガス浄化触媒用多孔質構造体。
- 触媒活性成分を含む、請求項1又は2に記載の排ガス浄化触媒用多孔質構造体。
- 基材と、該基材表面に形成された触媒層とを有する排ガス浄化触媒であって、
前記触媒層が酸素貯蔵成分及び無機多孔質体を含んでおり、
前記排ガス浄化触媒は、水銀圧入ポロシメータにより測定される細孔容積分布において、細孔径が5nm以上15nm未満の細孔容積に対する15nm以上25nm未満の細孔容積の比が1.3以上2.5以下である、排ガス浄化触媒。 - 前記細孔容積分布において、細孔径が15nm以上25nm未満の範囲内に少なくとも1つのピークトップを有する、請求項4に記載の排ガス浄化触媒。
- 前記細孔容積分布において、全細孔容積に対する細孔径が5nm以上15nm未満の細孔容積の割合が5%以上35%以下であり、全細孔容積に対する細孔径が15nm以上25nm未満の細孔容積の割合が10%以上50%以下である、請求項4又は5に記載の排ガス浄化触媒。
- 前記細孔容積分布において、細孔径が5nm以上200nm以下の細孔の細孔容積に対する細孔径が5nm以上15nm未満の細孔の細孔容積の割合が15%以上40%以下であり、細孔径が5nm以上200nm以下の細孔の細孔容積に対する細孔径が15nm以上25nm未満の細孔の細孔容積の割合が20%以上60%以下である、請求項4~6のいずれかに1項に記載の排ガス浄化触媒。
- 前記酸素貯蔵成分の含有量は前記無機多孔質体の含有量よりも多い、請求項4~7のいずれかに1項に記載の排ガス浄化触媒
- 前記触媒層中に触媒活性成分を含む、請求項4~8のいずれか1項に記載の排ガス浄化触媒。
- 請求項4~9のいずれか1項に記載の排ガス浄化触媒に内燃機関から排出された排ガスを接触せしめて排ガスを浄化する排ガス浄化方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/268,123 US11141721B2 (en) | 2018-08-22 | 2019-08-05 | Porous structure for exhaust gas purification catalyst, exhaust gas purification catalyst using porous structure, and exhaust gas purification method |
EP19852693.1A EP3842143B1 (en) | 2018-08-22 | 2019-08-05 | Porous structure for exhaust gas purification catalyst, exhaust gas purification catalyst using porous structure, and exhaust gas purification method |
JP2020531781A JP6803497B2 (ja) | 2018-08-22 | 2019-08-05 | 排ガス浄化触媒用多孔質構造体及びそれを用いた排ガス浄化触媒並びに排ガス浄化方法 |
KR1020217004219A KR102312699B1 (ko) | 2018-08-22 | 2019-08-05 | 배기 가스 정화 촉매용 다공질 구조체 및 그것을 사용한 배기 가스 정화 촉매 그리고 배기 가스 정화 방법 |
CN201980054226.0A CN112584928B (zh) | 2018-08-22 | 2019-08-05 | 废气净化催化剂用多孔结构体和使用其的废气净化催化剂以及废气净化方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018155789 | 2018-08-22 | ||
JP2018-155789 | 2018-08-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020039903A1 true WO2020039903A1 (ja) | 2020-02-27 |
Family
ID=69593054
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/030646 WO2020039903A1 (ja) | 2018-08-22 | 2019-08-05 | 排ガス浄化触媒用多孔質構造体及びそれを用いた排ガス浄化触媒並びに排ガス浄化方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11141721B2 (ja) |
EP (1) | EP3842143B1 (ja) |
JP (1) | JP6803497B2 (ja) |
KR (1) | KR102312699B1 (ja) |
CN (1) | CN112584928B (ja) |
WO (1) | WO2020039903A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115916403A (zh) * | 2020-06-30 | 2023-04-04 | 株式会社科特拉 | 排气净化用催化剂 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11344864B2 (en) * | 2018-11-12 | 2022-05-31 | Umicore Shokubai Japan Co., Ltd. | Diesel engine exhaust gas purification catalyst, production method therefor, and exhaust gas purification method using the same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11104493A (ja) * | 1997-10-02 | 1999-04-20 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及び使用方法 |
WO2006070540A1 (ja) * | 2004-12-27 | 2006-07-06 | Ibiden Co., Ltd. | セラミックハニカム構造体 |
US20080167181A1 (en) | 2007-01-10 | 2008-07-10 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and producing method thereof |
US20140371058A1 (en) | 2012-02-07 | 2014-12-18 | Honda Motor Co., Ltd. | Catalyst Structure for Treating Exhaust Gas |
WO2015037536A1 (ja) * | 2013-09-10 | 2015-03-19 | 新日鐵住金株式会社 | 酸化触媒、排ガス処理装置、蓄熱燃焼バーナー、ガス中の可燃成分を酸化する方法及びガス中の窒素酸化物の除去方法 |
US20160045896A1 (en) | 2013-03-29 | 2016-02-18 | Mitsui Mining & Smelting Co., Ltd. | Catalyst structure for exhaust gas treatment |
JP2017064627A (ja) * | 2015-09-30 | 2017-04-06 | 日揮触媒化成株式会社 | 排ガス処理用触媒およびその製造方法 |
WO2018012565A1 (ja) * | 2016-07-14 | 2018-01-18 | イビデン株式会社 | ハニカム構造体及び該ハニカム構造体の製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2663245B1 (fr) * | 1990-06-13 | 1992-09-18 | Rhone Poulenc Chimie | Composition a base d'alumine pour catalyseur et procede de fabrication. |
JP6438384B2 (ja) * | 2013-10-31 | 2018-12-12 | 三井金属鉱業株式会社 | 排ガス浄化触媒用担体及び排ガス浄化触媒 |
US10245579B2 (en) * | 2014-02-18 | 2019-04-02 | Nissan Motor Co., Ltd. | Exhaust gas purification catalyst and production method thereof |
JP6213508B2 (ja) | 2015-03-20 | 2017-10-18 | トヨタ自動車株式会社 | 触媒コンバーター |
JP6701581B2 (ja) * | 2017-03-02 | 2020-05-27 | 株式会社豊田中央研究所 | 酸素吸放出材 |
-
2019
- 2019-08-05 KR KR1020217004219A patent/KR102312699B1/ko active IP Right Grant
- 2019-08-05 US US17/268,123 patent/US11141721B2/en active Active
- 2019-08-05 JP JP2020531781A patent/JP6803497B2/ja active Active
- 2019-08-05 EP EP19852693.1A patent/EP3842143B1/en active Active
- 2019-08-05 CN CN201980054226.0A patent/CN112584928B/zh active Active
- 2019-08-05 WO PCT/JP2019/030646 patent/WO2020039903A1/ja unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11104493A (ja) * | 1997-10-02 | 1999-04-20 | Nissan Motor Co Ltd | 排気ガス浄化用触媒及び使用方法 |
WO2006070540A1 (ja) * | 2004-12-27 | 2006-07-06 | Ibiden Co., Ltd. | セラミックハニカム構造体 |
US20080167181A1 (en) | 2007-01-10 | 2008-07-10 | Nissan Motor Co., Ltd. | Exhaust gas purifying catalyst and producing method thereof |
US20140371058A1 (en) | 2012-02-07 | 2014-12-18 | Honda Motor Co., Ltd. | Catalyst Structure for Treating Exhaust Gas |
US20160045896A1 (en) | 2013-03-29 | 2016-02-18 | Mitsui Mining & Smelting Co., Ltd. | Catalyst structure for exhaust gas treatment |
WO2015037536A1 (ja) * | 2013-09-10 | 2015-03-19 | 新日鐵住金株式会社 | 酸化触媒、排ガス処理装置、蓄熱燃焼バーナー、ガス中の可燃成分を酸化する方法及びガス中の窒素酸化物の除去方法 |
JP2017064627A (ja) * | 2015-09-30 | 2017-04-06 | 日揮触媒化成株式会社 | 排ガス処理用触媒およびその製造方法 |
WO2018012565A1 (ja) * | 2016-07-14 | 2018-01-18 | イビデン株式会社 | ハニカム構造体及び該ハニカム構造体の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3842143A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115916403A (zh) * | 2020-06-30 | 2023-04-04 | 株式会社科特拉 | 排气净化用催化剂 |
Also Published As
Publication number | Publication date |
---|---|
CN112584928A (zh) | 2021-03-30 |
KR20210022763A (ko) | 2021-03-03 |
EP3842143A1 (en) | 2021-06-30 |
JPWO2020039903A1 (ja) | 2020-10-22 |
KR102312699B1 (ko) | 2021-10-15 |
US20210245147A1 (en) | 2021-08-12 |
US11141721B2 (en) | 2021-10-12 |
JP6803497B2 (ja) | 2020-12-23 |
EP3842143A4 (en) | 2021-06-30 |
CN112584928B (zh) | 2021-11-23 |
EP3842143B1 (en) | 2022-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6932149B2 (ja) | パラジウムディーゼル酸化触媒 | |
JP6733073B2 (ja) | 排ガス浄化触媒 | |
WO2014119749A1 (ja) | 排ガス浄化用触媒及び該触媒を用いた排ガス浄化方法 | |
JP6771119B2 (ja) | 排ガス浄化触媒 | |
KR20180085813A (ko) | 희박 가솔린 직접 분사 엔진을 위한 촉매 시스템 | |
JP6803497B2 (ja) | 排ガス浄化触媒用多孔質構造体及びそれを用いた排ガス浄化触媒並びに排ガス浄化方法 | |
JP7466535B2 (ja) | 排ガス浄化用触媒及び該排ガス浄化用触媒を用いた排ガス浄化システム | |
JP2019155363A (ja) | 内燃機関の排気ガスの浄化用触媒および該触媒を用いた排気ガスの浄化方法 | |
JP6824467B2 (ja) | 排ガス浄化用触媒 | |
WO2019187198A1 (ja) | 排ガス浄化用触媒 | |
CN110382110A (zh) | 结合铂族金属与铜-氧化铝尖晶石的催化剂 | |
JP6947954B1 (ja) | 排ガス浄化用触媒 | |
WO2024014409A1 (ja) | 排ガス浄化用触媒組成物、排ガス浄化用触媒及び排ガス浄化システム | |
WO2023085091A1 (ja) | 排ガス浄化触媒、排ガスの浄化方法、及び排ガス浄化触媒の製造方法 | |
WO2021145326A1 (ja) | 排ガス浄化システム | |
WO2020031508A1 (ja) | 排ガス浄化触媒用組成物及びそれを用いた排ガス浄化触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19852693 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020531781 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20217004219 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2019852693 Country of ref document: EP Effective date: 20210322 |