JP5935816B2 - 排気ガス浄化用触媒 - Google Patents
排気ガス浄化用触媒 Download PDFInfo
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- JP5935816B2 JP5935816B2 JP2014005184A JP2014005184A JP5935816B2 JP 5935816 B2 JP5935816 B2 JP 5935816B2 JP 2014005184 A JP2014005184 A JP 2014005184A JP 2014005184 A JP2014005184 A JP 2014005184A JP 5935816 B2 JP5935816 B2 JP 5935816B2
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- catalyst
- catalyst layer
- exhaust gas
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- layer
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- 239000003054 catalyst Substances 0.000 title claims description 273
- 238000000746 purification Methods 0.000 title description 39
- 239000007789 gas Substances 0.000 claims description 93
- 239000000463 material Substances 0.000 claims description 57
- 239000002131 composite material Substances 0.000 claims description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 29
- 229910000510 noble metal Inorganic materials 0.000 description 29
- 229910052717 sulfur Inorganic materials 0.000 description 29
- 239000011593 sulfur Substances 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000009825 accumulation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000012876 carrier material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005275 alloying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 208000005374 Poisoning Diseases 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 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
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 210000001316 polygonal cell Anatomy 0.000 description 1
- 230000005855 radiation Effects 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
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- Combustion & Propulsion (AREA)
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Description
本発明は、排気ガス浄化用触媒に関する。
本発明の排気ガス浄化用触媒の構成を示す模式図を図1に示す。図1に示すように、本発明の排気ガス浄化用触媒1は、基材11と、基材11上に配置された触媒層12を備えていることが必要であり、触媒層12はさらに、基材11上に配置された第1の触媒層13と、第1の触媒層13の上面に配置された第2の触媒層14とを備えることが必要である。
[I-1. リン酸アルミニウムの調製]
ビーカーに、150 mlのイオン交換水を注ぎ、撹拌子を投入した。このイオン交換水に、0.1 molの硝酸アルミニウム9水和物(ナカライテスク社製)を加えた後、撹拌しながら溶解させた。別のビーカーに、0.1 molのリン酸に相当する量の85質量%リン酸(ナカライテスク社製)を秤量した。秤量されたリン酸を、前記硝酸アルミニウム水溶液に撹拌しながら加えた。ビーカーに残留したリン酸を、イオン交換水で濯ぎ回収して、前記の混合水溶液に加えた。得られた混合水溶液に、28%アンモニア水(ナカライテスク社製)を、ピペットを用いて少量ずつ滴下して、pHが4.0となるように調整した。その後、混合水溶液のビーカーに蓋を載せ、室温で12時間撹拌した。次いで、混合水溶液を遠心分離(3000 rpm、10分)して、沈殿物及び上清に分離した。得られた沈殿物に適量のイオン交換水を加えて懸濁させた後、前記と同様の条件で遠心分離して、沈殿物及び上清に分離した。得られた沈殿物を、乾燥器を用いて120℃で12時間乾燥させた。得られた乾燥物を、乳鉢及び乳棒を用いて粉砕し、粉末状にした。この粉末を、電気炉を用いて1100℃で5時間焼成して、リン酸アルミニウムを得た。
ビーカーに、150 mlのイオン交換水を注ぎ、撹拌子を投入した。このイオン交換水に、所定量の硝酸白金水溶液(濃度:8.6質量%;使用量:9.5 g)を加えた後、撹拌した。前記水溶液に、下記に示す担体材料を40 g秤量して加えた後、撹拌した。得られた水溶液を撹拌しながら150℃で加熱し、水分を蒸発乾固させた。残留物を、乾燥器を用いて120℃で12時間乾燥させた。得られた乾燥物を、乳鉢及び乳棒を用いて粉砕し、粉末状にした。この粉末を、電気炉を用いて500℃で3時間焼成して、第1触媒層材料を得た。
ビーカーに、100 mlのイオン交換水を注ぎ、撹拌子を投入した。このイオン交換水に、所定量の硝酸ロジウム水溶液(濃度:2.75質量%;使用量:2.86 g)を加えた後、撹拌した。前記水溶液に、15 gの多孔質アルミナ(ランタン添加アルミナ)及び15 gの低熱劣化性セリア−ジルコニア複合酸化物を秤量して加えた後、撹拌した。得られた水溶液を撹拌しながら150℃で加熱し、水分を蒸発乾固させた。残留物を、乾燥器を用いて120℃で12時間乾燥させた。得られた乾燥物を、乳鉢及び乳棒を用いて粉砕し、粉末状にした。この粉末を、電気炉を用いて500℃で3時間焼成して、第2触媒層材料を得た。
[II-1. 第1触媒層の調製]
イオン交換水に、3.82 gの第1触媒層材料及び0.08 gのアルミナ系バインダーを加え、撹拌しながら一晩ミリングした。その後、得られた混合物の粘度を調整して、スラリーを得た。前記スラリーを、35 mL(L = 50 mm)のセラミックハニカムテストピース基材に流し入れて、基材内壁の表面にスラリーをコーティングした。スラリーでコーティングされた基材を、150℃に設定された乾燥器内で1時間静置して、スラリーの水分を蒸発させた。その後、基材を、500℃に設定された電気炉内で3時間静置して、基材及びコーティングを焼成した。これにより、第1触媒層(総被覆量:3.89 g;111.1 g/L基材)を調製した。
2.40 gの第2触媒層材料及び0.16 gのアルミナ系バインダーを用いて、前記II-1と同様の手順により、第2触媒層材料を含有するスラリーを調製した。得られたスラリーを、第1触媒層が形成された基材に流し入れて、第1触媒層の上面にスラリーをコーティングした。スラリーでコーティングされた基材を、250℃に設定された乾燥器内で1時間静置して、スラリーの水分を蒸発させた。その後、基材を、500℃に設定された電気炉内で3時間静置して、基材及びコーティングを焼成した。これにより、第2触媒層(総被覆量:2.56 g;73.1 g /L基材)を調製した。
[III-1. X線光電子分光分析]
JIS K 0147に基づき、X線光電子分光分析(XPS)装置(Al線源)(PHI 5000;フィリップス社製)を用いて、比較例1〜3、並びに実施例1及び2の触媒に用いた第1触媒層材料の表面にX線を照射することにより、第1触媒層材料の表面の電子状態を分析した。得られたXPSスペクトルから、O 1s結合エネルギー(eV)を決定した。
ガソリンエンジンを用いて、図2に示す温度条件で、比較例1〜3、並びに実施例1及び2の触媒の熱耐久処理を行った。ここで、ガス流量は、10 L/分の一定値とした。ガス組成は、(1)昇温工程及び(3)降温工程は、N2 = 100%のガス分圧とし、(2)保持工程は、CO/O2/H2O/N2 = 1/5/10/残部のガス分圧で、且つ5分間隔で、CO及びO2のうちどちらか一方のガス流通を停止させた。これにより、排気ガス組成を変動させて、触媒の劣化を促進させた。
ガソリンエンジンを用いて、図3に示す温度条件で、比較例1〜3、並びに実施例1及び2の触媒に用いた第1触媒層材料の硫黄被毒処理を行った。試料としては、各比較例及び実施例の第1触媒層材料を、1 gのペレットに成形したものを使用した。ここで、ガス流量は、5 L/分の一定値とした。ガス組成は、(1)昇温工程及び(3)降温工程は、N2 = 100%のガス分圧とし、(2)保持工程は、NO/CO/C3H6/CO2/O2/H2O/SO2/N2 = 0.1/0.65/0.1/10/0.725/3/0.05/残部のガス分圧とした。これにより、排気ガス組成を変動させて、触媒の劣化を促進させた。
前記III-3の手順に基づき、比較例1〜3、並びに実施例1及び2の触媒に用いた第1触媒層材料の硫黄被毒処理を行った。処理後の試料(ペレット)に含有される硫黄蓄積量を、C-S計(EMIA-820W;堀場製作所製)を用いて測定した。
前記III-2の手順に基づき、比較例1〜3、並びに実施例1及び2の触媒の熱耐久処理を行った。モデルガス装置を用いて、図4に示す温度条件で、熱耐久処理後の比較例1〜3、並びに実施例1及び2の触媒の活性を評価した。ここで、ガス流量は、30 L/分の一定値とした。ガス組成は、NO/CO/C3H6/CO2/O2/H2O/N2 = 0.19/0.95/0.15/9.5/0.41/4.73/残部のガス分圧とした。NOx浄化率は、以下の式から算出した。下記式中、流入ガス濃度は、触媒のガス流入部におけるNOx濃度を意味し、流出ガス濃度は、触媒のガス流出部におけるNOx濃度を意味する。
走査型電子顕微鏡(SEM)を用いて、比較例1〜3、並びに実施例1及び2の触媒の断面を撮影した。それぞれの触媒の断面において、基材の表面に形成された第1の触媒層及び第2の触媒層の厚さを、基材の内角部分は25箇所、直線部分は36箇所ずつ測定した。それぞれの触媒について、基材の内角部分及び直線部分における触媒層の厚さの平均値を算出した。
比較例1〜3、並びに実施例1及び2の触媒のそれぞれについて、前記の手順により、O 1s結合エネルギー、NOx50%浄化温度及び硫黄蓄積量を決定した。各触媒のO 1s結合エネルギーとNOx50%浄化温度との関係を図5に、O 1s結合エネルギーと硫黄蓄積量との関係を図6に、それぞれ示す。
11…基材
12…触媒層
13…第1の触媒層
14…第2の触媒層
Claims (5)
- 基材と、該基材の上面に配置され、アルミニウムとリン及びホウ素から選択される少なくとも1種の元素と酸素とからなり、530〜535 eVの範囲の酸素1s結合エネルギーを有する複合酸化物を含有する担体と該担体に担持された白金とを有する第1の触媒層と、該第1の触媒層の上面に配置され、低熱劣化性セリア−ジルコニア複合酸化物又は多孔質アルミナを含有する担体と該担体に担持されたロジウムとを有する第2の触媒層とを備える、排気ガス浄化用触媒。
- 前記第1の触媒層の担体が、リン酸アルミニウム又はホウ酸アルミニウムを含有する、請求項1に記載の排気ガス浄化用触媒。
- 前記複合酸化物が、ホウ酸アルミニウムである、請求項1又は2に記載の排気ガス浄化用触媒。
- 前記第1の触媒層の被覆量が、40〜150 g/L基材の範囲であり、前記第2の触媒層の被覆量が、30〜180 g/L基材の範囲である、請求項1〜3のいずれか1項に記載の排気ガス浄化用触媒。
- 前記第1の触媒層の厚さが、10〜100 μmの範囲であり、前記第2の触媒層の厚さが、10〜60 μmの範囲である、請求項1〜4のいずれか1項に記載の排気ガス浄化用触媒。
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