JP2009011937A - 排ガス浄化用触媒 - Google Patents
排ガス浄化用触媒 Download PDFInfo
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- JP2009011937A JP2009011937A JP2007176602A JP2007176602A JP2009011937A JP 2009011937 A JP2009011937 A JP 2009011937A JP 2007176602 A JP2007176602 A JP 2007176602A JP 2007176602 A JP2007176602 A JP 2007176602A JP 2009011937 A JP2009011937 A JP 2009011937A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000007789 gas Substances 0.000 claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 36
- 239000011232 storage material Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 17
- 239000010948 rhodium Substances 0.000 claims abstract description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 description 60
- 239000000843 powder Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 22
- 238000000746 purification Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 3
- 229960001633 lanthanum carbonate Drugs 0.000 description 3
- 230000001737 promoting effect Effects 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
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- -1 barium Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 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
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 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
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 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
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- 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
- 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
- B01D53/922—Mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/925—Simultaneous elimination of carbon monoxide or hydrocarbons and nitrogen oxides
-
- 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
- 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
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- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
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- B01D2255/1025—Rhodium
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- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/9022—Two layers
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/16—Oxygen
Abstract
【解決手段】本発明の排ガス浄化用触媒1は、基材2と、前記基材2を被覆すると共に酸素貯蔵材料とパラジウムとを含み、ロジウムを含んでいない下層3と、前記下層3を被覆すると共にロジウムとこれを担持した担体と含み、前記下層3と比較して酸素貯蔵能がより低い上層4とを具備したことを特徴とする。
【選択図】 図2
Description
図1は、本発明の一態様に係る排ガス浄化用触媒を概略的に示す斜視図である。図2は、図1に示す排ガス浄化用触媒に採用可能な構造の一例を概略的に示す断面図である。
例えば、下層3のうち、上層4側の部分は、基材2側の部分と比較してパラジウム含量がより大きくてもよい。この場合、下層3の基材2側の部分は、下層3の上層4側の部分と比較して酸素貯蔵能がより高く(例えばセリウム含量がより大きく)てもよい。このとき、下層3の基材2側の部分は、パラジウムを含んでいなくてもよい。また、下層3の基材2側の部分は、白金をさらに含んでいてもよい。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、下層3に、第1層と第2層とからなる二層構造を採用した。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、下層3に、第1層と第2層とからなる二層構造を採用した。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、下層3に、第1層と第2層とからなる二層構造を採用した。
以上のようにして、図1及び図2に示す排ガス浄化用触媒1を完成した。以下、この排ガス浄化用触媒1を触媒Cと呼ぶ。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。
まず、触媒Aについて説明したのと同様の方法により、モノリスハニカム基材2上に下層3を形成した。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、上層4に、第3層と第4層との二層構造を採用した。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、下層3に、第1層と第2層との二層構造を採用した。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。
まず、60gのアルミナ粉末と30gの酸化物粉末CZ1と30gの酸化物粉末CZ2とパラジウムを1.5g含有した硝酸パラジウム水溶液とを混合して、スラリーを調製した。以下、このスラリーを、スラリーS9と呼ぶ。
以上のようにして、図1及び図2に示す排ガス浄化用触媒1を完成した。以下、この排ガス浄化用触媒1を触媒Gと呼ぶ。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。
まず、30gの酸化物粉末とパラジウムを0.5g含有した硝酸パラジウム水溶液とを混合した。この混合物を250℃で8時間乾燥させ、続いて、500℃で1時間焼成した。以下、これにより得られた粉末を、粉末P1と呼ぶ。
以上のようにして、図1及び図2に示す排ガス浄化用触媒1を完成した。以下、この排ガス浄化用触媒1を触媒Hと呼ぶ。
本例では、図1及び図2に示す排ガス浄化用触媒1を、以下の方法で製造した。なお、本例では、下層3に、第1層と第2層との二層構造を採用した。
本例では、排ガス浄化用触媒を、以下の方法で製造した。
まず、30gのアルミナ粉末と30gの酸化物粉末CZ2とパラジウムを1.5g含有した硝酸パラジウム水溶液とを混合して、スラリーを調製した。以下、このスラリーを、スラリーS14と呼ぶ。
触媒A乃至Jの各々を、排気量が0.7Lのエンジンを有する自動車に搭載した。次いで、各自動車に、60000kmの耐久走行距離を走行させた。その後、10・15モード法及び11モード法により、非メタン炭化水素(NMHC)、CO及びNOxの各々について走行距離1km当たりの排出量を測定した。なお、NMHCの排出量は、炭素数等量による容量比で表した値をグラムに換算した値である。また、10・15モード法で得られた測定値には88/100を乗じ、11モード法で得られた測定値には12/100を乗じ、それらの合算値を求めた。その結果を、以下の表に纏める。
Claims (8)
- 基材と、
前記基材を被覆すると共に酸素貯蔵材料とパラジウムとを含み、ロジウムを含んでいない下層と、
前記下層を被覆すると共にロジウムとこれを担持した担体と含み、前記下層と比較して酸素貯蔵能がより低い上層とを具備したことを特徴とする排ガス浄化用触媒。 - 前記下層のうち、前記上層側の部分は、前記基材側の部分と比較してパラジウム含量がより大きいことを特徴とする請求項1に記載の排ガス浄化用触媒。
- 前記基材側の部分は、前記上層側の部分と比較してセリウム含量がより大きいことを特徴とする請求項2に記載の排ガス浄化用触媒。
- 前記基材側の部分はパラジウムを含んでいないことを特徴とする請求項3に記載の排ガス浄化用触媒。
- 前記基材側の部分は白金をさらに含んでいることを特徴とする請求項4に記載の排ガス浄化用触媒。
- 前記下層及び前記上層の少なくとも一方は、アルカリ土類金属及び/又は希土類元素をさらに含んだことを特徴とする請求項1乃至5の何れか1項に記載の排ガス浄化用触媒。
- 前記上層はパラジウムをさらに含んだことを特徴とする請求項1に記載の排ガス浄化用触媒。
- 前記上層のうち、前記下層側の部分は、表面側の部分と比較してロジウム含量がより大きく且つパラジウム含量がより小さいことを特徴とする請求項7に記載の排ガス浄化用触媒。
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CN101687180A (zh) | 2010-03-31 |
CN101687180B (zh) | 2013-06-26 |
US8039418B2 (en) | 2011-10-18 |
US20100087314A1 (en) | 2010-04-08 |
EP2163303A1 (en) | 2010-03-17 |
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