JP7026530B2 - 排ガス浄化用三元触媒 - Google Patents
排ガス浄化用三元触媒 Download PDFInfo
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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
- F01N3/101—Three-way catalysts
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- 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
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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
- 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
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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
- 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
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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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
- 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
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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
- 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
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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
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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
-
- 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
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
-
- 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
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- 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
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Description
(1)触媒担体と、前記触媒担体の少なくとも一方の面側に設けられた触媒層とを少なくとも備え、前記触媒層は、白金族元素を含む第1触媒層と、白金族元素を含む第2触媒層と、最表層の白金族元素を含む第3触媒層とをこの順に少なくとも有する積層構造を有し、前記第1触媒層は、第1母材粒子及び前記第1母材粒子上に少なくとも担持されたパラジウムを有する第1複合触媒粒子を少なくとも含有し、前記第2触媒層は、第2母材粒子及び前記第2母材粒子上に少なくとも担持されたロジウムを有する第2複合触媒粒子を少なくとも含有し、前記第3触媒層は、第3母材粒子及び前記第3母材粒子上に少なくとも担持されたパラジウムを有する第3複合触媒粒子を少なくとも含有し、前記第1乃至第3触媒層の総塗工量Wt(但し、各触媒層中に含まれる白金族元素を除く。)が、前記触媒担体の容積あたり、合計で110g/L以上225g/L以下である、排ガス浄化用三元触媒。
0.1Wt≦W1≦0.4Wt
を満たす(1)に記載の排ガス浄化用三元触媒。
(3)前記第1乃至第3触媒層の総塗工量Wt(但し、各触媒層中に含まれる白金族元素を除く。)が、前記触媒担体の容積あたり、合計で125g/L以上200g/L以下である(1)又は(2)に記載の排ガス浄化用三元触媒。
(4)前記触媒層中に含まれる白金族元素が、前記触媒担体の容積あたり、合計で1g/L以上10g/L以下である(1)~(3)のいずれか一項に記載の排ガス浄化用三元触媒。
(6)前記セリアジルコニア系複合酸化物は、構成金属元素としてNd及びPrを、酸化物換算で以下の質量割合;
CeO2 10~50質量%
ZrO2 40~80質量%
Nd2O3 0.1~10質量%
Pr5O11 0.1~10質量%
で含有する(5)に記載の排ガス浄化用三元触媒。
(7)前記第1母材粒子の前記セリアジルコニア系複合酸化物のCe含有割合が、CeO2換算で、前記第3母材粒子の前記セリアジルコニア系複合酸化物のCe含有割合よりも大きい(6)に記載の排ガス浄化用三元触媒。
(9)前記第2触媒層は、比表面積が50~300m2/gのアルミナをさらに含有する(1)~(8)のいずれか一項に記載の排ガス浄化用三元触媒。
(10)前記第1及び第3触媒層は、Ba含有化合物をさらに含有する(1)~(9)のいずれか一項に記載の排ガス浄化用三元触媒。
(12)前記第1乃至第3触媒層中に含まれるパラジウム及びロジウムの質量割合が、合計でPd:Rh=4~20:1の範囲内にある(1)~(11)のいずれか一項に記載の排ガス浄化用三元触媒。
CeO2 10~50質量%
ZrO2 40~80質量%
Nd2O3 0.1~10質量%
Pr5O11 0.1~10質量%
CeO2 35~50質量%
ZrO2 40~60質量%
Nd2O3 0.1~10質量%
Pr5O11 0.1~10質量%
また、第3母材粒子としては、他の希土類元素がドープされたセリアジルコニア系複合酸化物であって、構成金属元素としてNd及びPrを、酸化物換算で以下の質量割合で含有するものが特に好ましい。
CeO2 10~34質量%
ZrO2 40~80質量%
Nd2O3 0.1~10質量%
Pr5O11 0.1~10質量%
合計で2.5g/L以上5.0g/L以下である。
γ-アルミナ粉末(BET比表面積150m2/g、平均粒子径D50=10μm)33質量部、並びに、Nd及びPr固溶セリア-ジルコニア系複合酸化物(CeZrNdPr酸化物1と記載、Nd2O3:7質量%、Pr5O11:7質量%、CeO2:40質量%、ZrO2:45質量%、平均粒子径D50=10μm)67質量部に、硝酸パラジウム(II)溶液(Pd換算で20質量%含有)を含浸させ、600℃で30分間焼成して、第1複合触媒粒子を得た。
白金族元素の含有量(塗工量)を変えずに各母材粒子の塗工量を表1に示すとおり変更する以外は、実施例1と同様に行い、耐久処理後の実施例2~4及び比較例1~4の排ガス浄化用三元触媒を得た。
耐久処理後の排ガス浄化用三元触媒をそれぞれ用いて、HC浄化率のライトオフ試験を行った。ここでは、2Lエンジンを用い、エンジン回転数1950rpm、ブースト圧-280mmHg、A/Fレート14.56±0.1/2.5Hzの条件下、触媒入口端面から1インチ部分に温度センサを取り付け、バイパス切り替えで450℃に保った排ガスを導入し、開始温度30℃から昇温成り行きで測定を行った。HC浄化率の測定結果を、図2に示す。また、このときのHCT50(HC浄化率が50%となるまでにかかった時間)と触媒層の塗工量Wtとの関係を図3に示す。
11 ・・・触媒担体
11a・・・面
11b・・・面
21 ・・・触媒層
L1 ・・・第1触媒層
L2 ・・・第2触媒層
L3 ・・・第3触媒層
Claims (5)
- 触媒担体と、前記触媒担体の少なくとも一方の面側に設けられた触媒層とを少なくとも備え、
前記触媒層は、白金族元素を含む第1触媒層と、白金族元素を含む第2触媒層と、最表層の白金族元素を含む第3触媒層とをこの順に少なくとも有する積層構造を有し、
前記第1触媒層は、第1母材粒子及び前記第1母材粒子上に少なくとも担持されたパラジウムを有する第1複合触媒粒子を少なくとも含有し、
前記第2触媒層は、第2母材粒子及び前記第2母材粒子上に少なくとも担持されたロジウムを有する第2複合触媒粒子を少なくとも含有し、
前記第3触媒層は、第3母材粒子及び前記第3母材粒子上に少なくとも担持されたパラジウムを有する第3複合触媒粒子を少なくとも含有し、
前記第1乃至第3触媒層の総塗工量Wt(但し、各触媒層中に含まれる白金族元素を除く。)が、前記触媒担体の容積あたり、合計で110g/L以上225g/L以下であり、
前記第1乃至第3母材粒子は、スカンジウム、イットリウム、ランタン、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロビウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、及びルテチウムよりなる群から選択される少なくとも1種の希土類元素がドープされたセリアジルコニア系複合酸化物からなる酸素吸蔵放出材料を含有する、
排ガス浄化用三元触媒。 - 前記第1触媒層の塗工量W1(但し、第1触媒層に含まれる白金族元素を除く。)が、前記第1乃至第3触媒層の総塗工量Wt(但し、各触媒層中に含まれる白金族元素を除く。)に対して、下記の関係;
0.1Wt≦W1≦0.4Wt
を満たす
請求項1に記載の排ガス浄化用三元触媒。 - 前記セリアジルコニア系複合酸化物は、構成金属元素としてNd及びPrを、酸化物換算で以下の質量割合;
CeO2 10~50質量%
ZrO2 40~80質量%
Nd2O3 0.1~10質量%
Pr5O11 0.1~10質量%
で含有する
請求項1に記載の排ガス浄化用三元触媒。 - 前記第1母材粒子の前記セリアジルコニア系複合酸化物のCe含有割合が、CeO2換算で、前記第3母材粒子の前記セリアジルコニア系複合酸化物のCe含有割合よりも大きい
請求項3に記載の排ガス浄化用三元触媒。 - 前記第1及び第3触媒層は、Ba含有化合物をさらに含有する
請求項1~4のいずれか一項に記載の排ガス浄化用三元触媒。
Priority Applications (4)
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JP2018029838A JP7026530B2 (ja) | 2018-02-22 | 2018-02-22 | 排ガス浄化用三元触媒 |
PCT/JP2019/002773 WO2019163435A1 (ja) | 2018-02-22 | 2019-01-28 | 排ガス浄化用三元触媒 |
US16/962,675 US11376568B2 (en) | 2018-02-22 | 2019-01-28 | Exhaust gas-purifying three-way catalyst |
CN201980006581.0A CN111491731B (zh) | 2018-02-22 | 2019-01-28 | 废气净化用三元催化剂 |
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JP7315164B2 (ja) * | 2019-03-29 | 2023-07-26 | 株式会社キャタラー | 触媒材料 |
US11541373B2 (en) * | 2019-11-19 | 2023-01-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Mixed oxide catalyst for oxygen storage applications and a method for making the catalyst |
JP7248616B2 (ja) * | 2020-03-25 | 2023-03-29 | トヨタ自動車株式会社 | 排ガス浄化用触媒 |
JPWO2022131244A1 (ja) * | 2020-12-15 | 2022-06-23 | ||
EP4052787A1 (en) * | 2021-03-02 | 2022-09-07 | Johnson Matthey Public Limited Company | Nox storage material |
WO2022209532A1 (ja) * | 2021-03-30 | 2022-10-06 | 三井金属鉱業株式会社 | 排ガス浄化用触媒組成物及び排ガス浄化用触媒 |
Citations (4)
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US20090175773A1 (en) | 2008-01-08 | 2009-07-09 | Chen Shau-Lin F | Multilayered Catalyst Compositions |
JP2010501337A (ja) | 2006-08-21 | 2010-01-21 | ビーエーエスエフ、カタリスツ、エルエルシー | 層状触媒複合材料 |
JP2015073943A (ja) | 2013-10-09 | 2015-04-20 | トヨタ自動車株式会社 | 触媒コンバーター |
WO2017222017A1 (ja) | 2016-06-23 | 2017-12-28 | エヌ・イーケムキャット株式会社 | リーンバーン用触媒 |
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