WO2014171443A1 - 排気ガス浄化用触媒 - Google Patents
排気ガス浄化用触媒 Download PDFInfo
- Publication number
- WO2014171443A1 WO2014171443A1 PCT/JP2014/060691 JP2014060691W WO2014171443A1 WO 2014171443 A1 WO2014171443 A1 WO 2014171443A1 JP 2014060691 W JP2014060691 W JP 2014060691W WO 2014171443 A1 WO2014171443 A1 WO 2014171443A1
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- Prior art keywords
- palladium
- platinum
- supported
- carrier
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000000746 purification Methods 0.000 title claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 125
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 58
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 93
- 239000000463 material Substances 0.000 description 50
- 239000000843 powder Substances 0.000 description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 39
- 239000007789 gas Substances 0.000 description 39
- 239000011248 coating agent Substances 0.000 description 31
- 238000000576 coating method Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 19
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 17
- 239000002585 base Substances 0.000 description 15
- 229910052703 rhodium Inorganic materials 0.000 description 15
- 239000010948 rhodium Substances 0.000 description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 15
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 10
- 239000011232 storage material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- -1 comprising a carrier Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 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
- 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
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- 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
-
- B01J35/396—
-
- B01J35/56—
-
- 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
-
- 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
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/91—NOx-storage component incorporated in the catalyst
-
- 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
- B01D2258/014—Stoichiometric gasoline engines
-
- 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
-
- 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.
- Exhaust gas discharged from an internal combustion engine such as an engine contains harmful substances such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Since these substances cause air pollution, it is necessary to purify the exhaust gas.
- harmful substances such as hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx). Since these substances cause air pollution, it is necessary to purify the exhaust gas.
- Exhaust gas can be purified using an exhaust gas purification catalyst.
- the exhaust gas purifying catalyst is usually composed of a base material and a catalyst layer disposed on the base material, and the catalyst layer includes a support and a catalyst metal supported on the support.
- noble metals such as platinum, palladium and rhodium are used as the catalyst metal.
- Patent Document 1 discloses an exhaust gas purifying catalyst for purifying NOx.
- the catalyst includes a base material, a lower catalyst layer and an upper catalyst layer disposed on the base material, the lower catalyst layer includes rhodium, and the upper catalyst layer includes at least one of platinum and palladium and rhodium. Is included.
- Patent Document 2 also discloses an exhaust gas purifying catalyst for purifying NOx.
- the catalyst includes a base material, a lower catalyst layer and an upper catalyst layer disposed on the base material, the lower catalyst layer includes rhodium, and the upper catalyst layer includes platinum and palladium.
- Patent Documents 1 and 2 As disclosed in Patent Documents 1 and 2, many exhaust gas purifying catalysts for purifying NOx are known. However, there is still a need for further improvement in NOx purification performance.
- an object of the present invention is to provide a new exhaust gas purification catalyst having excellent NOx purification performance.
- Platinum used for purification of exhaust gas causes sintering and particle size increases when used for a long time. Thereby, the catalytic activity of platinum decreases, and the NOx purification performance decreases.
- platinum sintering can be significantly suppressed by supporting platinum and palladium on the same carrier at a certain ratio. As a result, a decrease in the catalytic activity of platinum can be suppressed, and excellent NOx purification performance can be achieved.
- the present invention includes the following.
- a substrate [1] a substrate; and a catalyst layer including a first carrier, platinum supported on the first carrier, and a first palladium disposed on the substrate; Including An exhaust gas purifying catalyst, wherein a weight ratio of the platinum and the first palladium is 3: 1 to 8: 1.
- the catalyst layer further includes a second carrier and second palladium supported on the second carrier, and platinum is not supported on the second carrier, [1] or [ [2]
- a new exhaust gas purification catalyst excellent in NOx purification performance can be provided.
- An example of the exhaust gas purifying catalyst is shown. A part of sectional drawing of the catalyst for exhaust gas purification is shown. A part of sectional drawing of the catalyst for exhaust gas purification is shown. The relationship between the weight ratio of platinum on the first carrier and the first palladium and the NOx purification rate is shown. The relationship between the weight ratio of platinum on the first carrier to the first carrier and the NOx purification rate is shown. The relationship between the presence or absence of second palladium and the NOx purification rate is shown. The relationship between the weight ratio of platinum and first palladium on the first support and the particle size of platinum is shown. The relationship between the weight ratio of platinum and first palladium on the first carrier and the amount of NO 2 produced is shown.
- the present invention includes a substrate; and a catalyst layer that is disposed on the substrate and includes a first support, platinum supported on the first support, and first palladium.
- the present invention relates to an exhaust gas purifying catalyst having a weight ratio with the first palladium of 3: 1 to 8: 1.
- platinum and palladium are supported on the same carrier at a constant ratio, so that sintering of the platinum is greatly suppressed. As a result, a decrease in the catalytic activity of platinum is suppressed, and excellent NOx purification performance is obtained.
- the exhaust gas purifying catalyst according to the present invention can preferentially purify NOx even in a lean atmosphere.
- HC and CO emissions are small, but NOx emissions are very large, so a general three-way catalyst cannot sufficiently purify NOx.
- the exhaust gas purifying catalyst according to the present invention it is possible to efficiently purify NOx discharged from the lean burn engine while suppressing a decrease in the catalytic activity of platinum.
- Examples of the base material of the exhaust gas purification catalyst according to the present invention include those generally used in exhaust gas purification catalysts.
- a straight flow type or wall flow type monolith substrate may be used.
- the material of the base material is not particularly limited, and examples thereof include base materials such as ceramic, silicon carbide, and metal.
- the catalyst layer disposed on the substrate contains the first carrier, platinum and first palladium supported on the first carrier.
- the weight ratio of platinum supported on the first carrier with respect to the first carrier is not particularly limited, but is preferably 0.04 or less. By supporting platinum at such a weight ratio, the NOx purification performance can be further improved. Although the minimum of the weight ratio of the said platinum is not specifically limited, For example, 0.001, 0.005 etc. can be mentioned.
- the amount of platinum supported on the first carrier is not particularly limited, but is preferably 0.1 to 2 g per liter of the base material from the viewpoint of efficiently purifying NOx and the viewpoint of production cost. It is more preferably 0.5 to 1.8 g, particularly preferably 0.8 to 1.6 g.
- the catalyst layer disposed on the substrate may contain any other component in addition to the first carrier and platinum and first palladium supported on the first carrier.
- the catalyst layer may further include a second carrier and a second palladium supported on the second carrier. It is preferable that platinum is not supported on the second carrier.
- the catalyst layer may further contain rhodium. When the catalyst layer contains rhodium, rhodium is preferably supported on a carrier different from the first and second carriers.
- the first carrier, the second carrier, and the carrier supporting rhodium may be the same type of carrier or different types of carriers.
- the weight ratio of the first palladium to the second palladium is not particularly limited, but is preferably 1: 0.5 to 1: 3. By setting such a weight ratio, the NOx purification performance can be further improved.
- the total amount of palladium contained in the catalyst layer is not particularly limited, but is preferably 0.1 to 1 g per liter of the base material from the viewpoint of efficiently purifying NOx and the manufacturing cost, and 0.2 to It is more preferably 0.8 g, and particularly preferably 0.4 to 0.6 g.
- the amount of rhodium contained in the catalyst layer is not particularly limited, but is preferably 0.1 to 2 g per liter of the base material from the viewpoint of efficiently purifying NOx and the manufacturing cost. 0.5 g is more preferable, and 0.1 to 1.2 g is particularly preferable.
- examples of the carrier include zirconia, alumina, titania, silica, ceria, magnesia and the like.
- examples of the carrier include composite oxides of cerium and at least one selected from the group consisting of zirconium, hafnium, neodymium, yttrium, lanthanum, praseodymium, and nickel.
- One type of carrier may be used alone, or two or more types may be used in combination.
- the catalyst layer may further contain a substance having a function of storing NOx (hereinafter referred to as “NOx storage substance”).
- NOx storage substances include alkali metals, alkaline earth metals, and rare earth elements.
- alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium.
- Alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radium.
- rare earth elements include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
- the NOx storage material may be supported on the support, or may be present in the catalyst layer without being supported on the support. One type of NOx storage material may be used alone, or two or more types may be used in combination.
- the amount of the NOx occlusion substance is not particularly limited, but from the viewpoint of efficiently purifying NOx, it is preferably 0.01 to 5 mol, more preferably 0.05 to 1 mol, per 1 L of the substrate. Particularly preferred is 1 to 0.5 mol.
- the weight ratio of platinum supported on the first carrier and the first palladium is 3: 1 to 8: 1.
- the oxidation performance of NOx can be improved and NO 2 can be efficiently generated.
- oxygen is excessively present, so it is difficult to purify (reduce) NOx.
- NOx was oxidized to NO 2 in the lean atmosphere, the NO 2 by keeping by the NOx occluding substance, it is possible to reduce the emission of NOx.
- a reducing agent HC, CO, etc.
- the exhaust gas purifying catalyst according to the present invention is mainly composed of a base material and a catalyst layer, but may contain any layer within a range not impairing the effects of the present invention.
- an arbitrary layer may be included between the base material and the catalyst layer.
- the catalyst layer may be a single catalyst layer (FIG. 2) or may be composed of a plurality of catalyst layers. Although it does not specifically limit, it is preferable that a catalyst layer contains the lower layer catalyst layer arrange
- the catalyst layer contains rhodium
- rhodium, platinum and the first palladium are present in different catalyst layers.
- rhodium is preferably present in the lower catalyst layer
- platinum and first palladium are preferably present in the upper catalyst layer.
- the catalyst layer contains the second palladium
- the second palladium, platinum and the first palladium are present in the same catalyst layer.
- the second palladium, platinum and the first palladium are present in the upper catalyst layer.
- the NOx storage material is preferably present in both the upper catalyst layer and the lower catalyst layer.
- Base material As one embodiment of the present invention, Base material; A lower catalyst layer disposed on the substrate, comprising a carrier, rhodium supported on the carrier, and a NOx storage material; and a first carrier and the first catalyst disposed on the lower catalyst layer.
- An upper catalyst layer comprising platinum and first palladium supported on a carrier of the catalyst and a NOx storage material; And an exhaust gas purifying catalyst in which the weight ratio of the platinum to the first palladium is 3: 1 to 8: 1.
- Base material As another embodiment of the present invention, Base material; A lower catalyst layer disposed on the substrate, comprising a carrier, rhodium supported on the carrier, and a NOx storage material; and a first carrier and the first catalyst disposed on the lower catalyst layer.
- An upper catalyst layer comprising platinum and first palladium supported on the carrier, a second carrier, the second palladium supported on the second carrier, and a NOx storage material; And an exhaust gas purifying catalyst in which the weight ratio of the platinum to the first palladium is 3: 1 to 8: 1 and platinum is not supported on the second carrier. .
- Example 1 ⁇ Manufacture of exhaust gas purification catalyst> [Example 1] Zirconia (30 g) was suspended in water, and then rhodium nitrate was added. The mixture was evaporated to dryness to obtain rhodium-supported powder. The amount of rhodium supported on zirconia is 1% by weight.
- Alumina (10 g) (first carrier) was suspended in water, and then platinum nitrate and palladium nitrate (first palladium) were added at a weight ratio of 3: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder.
- the supported amounts of platinum and palladium on alumina are 10% by weight and 3.3% by weight, respectively.
- Alumina (5 g) (second carrier) was suspended in water, and then palladium nitrate (second palladium) was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 3.4% by weight.
- the coating material [1-1] was coated on the monolith substrate (1L) and baked to form a lower catalyst layer.
- a coating material [1-2] was coated on the lower catalyst layer and baked to form an upper catalyst layer.
- Barium and potassium were contained in the lower catalyst layer and the upper catalyst layer. The barium and potassium contents per liter of monolith substrate are both 0.1 mol.
- Example 2 (1) Alumina (10 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 5: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 10% by weight and 2% by weight, respectively.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 6% by weight.
- Example 3 (1) Alumina (10 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 8: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 10% by weight and 1.25% by weight, respectively.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 7.5% by weight.
- Example 4 (1) Alumina (25 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 3: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 4% by weight and 1.32% by weight, respectively.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 3.4% by weight.
- Example 5 (1) Alumina (45 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 3: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 2.22% by weight and 0.733% by weight, respectively.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 3.4% by weight.
- Example 6 (1) Alumina (45 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 3: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 2.22% by weight and 0.733% by weight, respectively.
- Example 7 (1) Alumina (10 g) was suspended in water, and then platinum nitrate and palladium nitrate were added at a weight ratio of 3: 1 (Pt: Pd). The mixture was evaporated to dryness to obtain a platinum-palladium supported powder. The supported amounts of platinum and palladium on alumina are 10% by weight and 3.3% by weight, respectively.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 1% by weight.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 8% by weight.
- Alumina (5 g) was suspended in water, and then palladium nitrate was added. The mixture was evaporated to dryness to obtain a palladium-supported powder. The amount of palladium supported on alumina is 10% by weight.
- NOx concentration and NO concentration were measured, and NO oxidation ability (NO 2 concentration) was evaluated from the difference.
Abstract
Description
前記基材上に配置された、第1の担体と当該第1の担体上に担持された白金及び第1のパラジウムとを含む触媒層;
を含み、
前記白金と前記第1のパラジウムとの重量比が3:1~8:1である、排気ガス浄化用触媒。
基材;
前記基材上に配置された、担体と当該担体上に担持されたロジウムと、NOx吸蔵物質とを含む下層触媒層;及び
前記下層触媒層上に配置された、第1の担体と当該第1の担体上に担持された白金及び第1のパラジウムと、NOx吸蔵物質とを含む上層触媒層;
を含み、前記白金と前記第1のパラジウムとの重量比が3:1~8:1である、排気ガス浄化用触媒を挙げることができる。
基材;
前記基材上に配置された、担体と当該担体上に担持されたロジウムと、NOx吸蔵物質とを含む下層触媒層;及び
前記下層触媒層上に配置された、第1の担体と当該第1の担体上に担持された白金及び第1のパラジウムと、第2の担体と当該第2の担体上に担持された第2のパラジウムと、NOx吸蔵物質とを含む上層触媒層;
を含み、前記白金と前記第1のパラジウムとの重量比が3:1~8:1であり、前記第2の担体上に白金が担持されていない、排気ガス浄化用触媒を挙げることができる。
[実施例1]
(1)水にジルコニア(30g)を懸濁させ、その後、硝酸ロジウムを加えた。混合物を蒸発乾固し、ロジウム担持粉末を得た。ジルコニアに対するロジウムの担持量は1重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを5:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ10重量%及び2重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを8:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ10重量%及び1.25重量%である。
(1)水にアルミナ(25g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを3:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ4重量%及び1.32重量%である。
(1)水にアルミナ(45g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを3:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ2.22重量%及び0.733重量%である。
(1)水にアルミナ(45g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを3:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ2.22重量%及び0.733重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを3:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ10重量%及び3.3重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを2.2:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ10重量%及び4.5重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金及び硝酸パラジウムを10:1(Pt:Pd)の重量比で加えた。混合物を蒸発乾固し、白金-パラジウム担持粉末を得た。アルミナに対する白金及びパラジウムの担持量はそれぞれ10重量%及び1重量%である。
(1)水にアルミナ(10g)を懸濁させ、その後、硝酸白金を加えた。混合物を蒸発乾固し、白金担持粉末を得た。アルミナに対する白金の担持量は10重量%である。
(1)各実施例及び比較例で製造した排気ガス浄化用触媒をコンバーターに内蔵した。触媒内蔵コンバーターを2Lエンジンに取り付け、触媒床温750℃及びストイキオメトリーで150時間耐久試験を行った。
Claims (3)
- 基材;及び
前記基材上に配置された、第1の担体と当該第1の担体上に担持された白金及び第1のパラジウムとを含む触媒層;
を含み、
前記白金と前記第1のパラジウムとの重量比が3:1~8:1である、排気ガス浄化用触媒。 - 第1の担体に対する、当該第1の担体上に担持された白金の重量比が0.04以下である、請求項1に記載の排気ガス浄化用触媒。
- 触媒層が、第2の担体と当該第2の担体上に担持された第2のパラジウムとを更に含み、前記第2の担体上に白金が担持されていない、請求項1又は2に記載の排気ガス浄化用触媒。
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EP14784916.0A EP2992955B1 (en) | 2013-04-19 | 2014-04-15 | Exhaust-gas purification catalyst |
CN201480021826.4A CN105121006B (zh) | 2013-04-19 | 2014-04-15 | 排气净化用催化剂 |
BR112015025876-0A BR112015025876B1 (pt) | 2013-04-19 | 2014-04-15 | catalisador de purificação de gás de escape |
US14/785,028 US9522385B2 (en) | 2013-04-19 | 2014-04-15 | Exhaust gas purifying catalyst |
ZA2015/08158A ZA201508158B (en) | 2013-04-19 | 2015-11-04 | Exhaust gas purifying catalyst |
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GB2554859A (en) * | 2016-10-04 | 2018-04-18 | Johnson Matthey Plc | NOx adsorber catalyst |
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See also references of EP2992955A4 |
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Publication number | Publication date |
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BR112015025876A2 (pt) | 2017-07-25 |
EP2992955A4 (en) | 2017-01-18 |
EP2992955A1 (en) | 2016-03-09 |
US9522385B2 (en) | 2016-12-20 |
BR112015025876B1 (pt) | 2020-11-10 |
JP5676679B2 (ja) | 2015-02-25 |
EP2992955B1 (en) | 2020-12-23 |
BR112015025876A8 (pt) | 2019-09-10 |
US20160074836A1 (en) | 2016-03-17 |
JP2014210238A (ja) | 2014-11-13 |
CN105121006A (zh) | 2015-12-02 |
CN105121006B (zh) | 2017-05-10 |
ZA201508158B (en) | 2017-09-27 |
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