WO2011118047A1 - 排ガス浄化用触媒 - Google Patents
排ガス浄化用触媒 Download PDFInfo
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- WO2011118047A1 WO2011118047A1 PCT/JP2010/055774 JP2010055774W WO2011118047A1 WO 2011118047 A1 WO2011118047 A1 WO 2011118047A1 JP 2010055774 W JP2010055774 W JP 2010055774W WO 2011118047 A1 WO2011118047 A1 WO 2011118047A1
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- catalyst layer
- nox occlusion
- nox
- exhaust gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 230000002860 competitive effect Effects 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000011232 storage material Substances 0.000 abstract description 3
- 239000002585 base Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 37
- 239000007789 gas Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 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
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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
- 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
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- B01J37/02—Impregnation, coating or precipitation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- 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
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- 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
- F01N3/0842—Nitrogen oxides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- 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
- F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
- F01N3/106—Auxiliary oxidation catalysts
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- B01D—SEPARATION
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- B01D2255/90—Physical characteristics of catalysts
- B01D2255/91—NOx-storage component incorporated in the catalyst
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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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- 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
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- 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, and more particularly to an exhaust gas purification catalyst provided with a NOx occlusion reduction type catalyst layer.
- NOx occlusion reduction type catalysts are subject to competitive adsorption of HC, CO, and NOx, and it has been difficult to ensure sufficient purification performance.
- a plurality of NOx occlusion reduction type catalysts having a two-layer coating structure have been reported in JP2009-101252A, etc.
- both upper and lower layers contain NOx occlusion material (or NOx retention material)
- HC Further, competitive adsorption of CO and NOx occurs, the active point of the NOx occlusion reduction reaction decreases, and the problem that the NOx occlusion reduction type catalyst cannot be made effective has not been solved.
- An object of the present invention is to provide an exhaust gas purifying catalyst having a structure capable of preventing the competitive adsorption of HC, CO, and NOx and efficiently utilizing the NOx occlusion reduction type catalyst.
- the exhaust gas purifying catalyst of the present invention comprises, on a base material, at least one NOx storage material selected from alkali metals or alkaline earth metals, and Pt and / or Rh.
- a NOx occlusion reduction type catalyst layer containing, An oxidation catalyst layer supporting Pt and / or Pd is provided on the NOx occlusion reduction type catalyst layer.
- the length of the oxidation catalyst layer is 25 to 60% of the length of the NOx occlusion reduction type catalyst layer when viewed in the direction of the exhaust gas flow.
- the oxidation catalyst layer has a thickness of 20 to 40 ⁇ m.
- FIG. 1 schematically shows HC, CO, and NOx that cause competitive adsorption in a NOx occlusion reduction type catalyst layer in a conventional exhaust gas purification catalyst.
- FIG. 2 shows a state in which HC and CO are selectively oxidized in the upper oxidation catalyst layer and NOx is selectively occluded and reduced in the lower NOx occlusion reduction type catalyst layer in the exhaust gas purification catalyst of the present invention.
- 3A and 3B are schematic diagrams respectively showing (A) a configuration image of the catalyst according to the present invention for laboratory evaluation and a conventional catalyst and (B) a configuration image of a catalyst according to the present invention for actual device evaluation.
- FIG. 4 is a graph showing a test cycle for laboratory evaluation.
- FIG. 5 is a graph showing NOx occlusion characteristics in the laboratory for the catalysts of the present invention and the conventional example.
- FIG. 6 is a graph showing NOx occlusion characteristics in an actual machine for the catalyst of the present invention.
- the upper and lower two layers are NOx occlusion reduction type catalyst layers, and as shown in FIG. 1, competitive adsorption of HC, CO, and NOx occurs, and the active point of the NOx occlusion reduction reaction is
- the NOx occlusion reduction type catalyst layer could not be effectively used. That is, even if the NOx occlusion reduction catalyst has a sufficient NOx occlusion capacity, the NOx occlusion speed at the occlusion start stage is slow, and the mode emission cannot exhibit sufficient performance. As a countermeasure, even when an oxidation catalyst is arranged upstream of the NOx occlusion reduction catalyst, the NOx occlusion speed is still slow when compared with the same capacity.
- the active point of the lower NOx occlusion reduction type catalyst layer is determined as NOx occlusion. It can be used effectively for the reduction reaction.
- the present invention can effectively utilize the lower NOx occlusion reduction type catalyst layer by providing the oxidation catalyst layer on the NOx occlusion reduction type catalyst layer. That is, the upper oxidation catalyst layer through which the exhaust gas first passes selectively oxidizes HC (hydrocarbon) and CO (carbon monoxide) that inhibit the reaction of the NOx storage reduction catalyst.
- the NOx occlusion speed of the NOx occlusion reduction type catalyst layer becomes maximum.
- the thickness of the oxidation catalyst layer is 20 to 40 ⁇ m. Within this range, the NOx occlusion speed of the NOx occlusion reduction type catalyst layer becomes maximum.
- the oxidation catalyst layer that overcoats the upper layer includes Pt and / or Pd having excellent catalytic ability as an oxidation catalyst in order to enhance oxidation performance.
- Rh that hinders the catalytic activity in the lean combustion gas is not added, and no NOx storage material that affects the noble metal activity is added.
- the NOx occlusion reduction type catalyst layer includes Pt and / or Rh and a NOx occlusion material. In particular, Rh and NOx occlusion material are added only to the lower NOx occlusion reduction type catalyst layer.
- DOC represents an oxidation catalyst layer
- NSR represents a NOx occlusion reduction type catalyst layer
- DOC oxidation catalyst layer
- the catalyst size is 35 cc (full length 50 mm) for the laboratory and 14 L (full length 110 mm) for the actual machine.
- the catalyst was subjected to simple durability at 700 ° C. ⁇ 27 h in an electric furnace.
- Three types of catalysts having the coating specifications shown in Table 1 were subjected to the test with the following constitution.
- FIG. 6 summarizes the results of the actual machine NOx storage test.
- the overcoat ratio was 55% (constant), and the overcoat amount was changed in the range of 24 to 72 g / L.
- the NOx occlusion rate was the highest when the overcoat amount was around 30 g / L.
- the optimum overcoat amount is in the range of 25 to 35 g / L with 30 g / L as the center. When this is converted into an overcoat thickness with respect to an overcoat ratio of 55%, the optimum overcoat thickness is about 20 to 40 ⁇ m.
- an exhaust gas purifying catalyst having a structure capable of preventing the competitive adsorption of HC, CO and NOx and efficiently utilizing the NOx occlusion reduction type catalyst.
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Abstract
Description
その解決のために、特開2009−101252等に2層コート構造を有するNOx吸蔵還元型触媒が複数報告されているが、上下2層共にNOx吸蔵材(あるいはNOx保持物質)を含むため、HC、CO、NOxの競争吸着が生じ、NOx吸蔵還元反応の活性点が減少してしまい、NOx吸蔵還元型触媒を有効に出来ないという問題は解消されなかった。
上記の目的を達成するために、本発明の排ガス浄化用触媒は、基材上に、アルカリ金属またはアルカリ土類金属から選択された少なくとも1種のNOx吸蔵材と、Ptおよび/またはRhとを含むNOx吸蔵還元型触媒層を備え、
前記NOx吸蔵還元型触媒層の上に、Ptおよび/またはPdを担持した酸化触媒層を備えた
ことを特徴とする。
望ましい形態においては、排ガス流の方向に見て、前記酸化触媒層の長さが前記NOx吸蔵還元型触媒層の長さの25~60%である。
望ましい形態においては、前記酸化触媒層の厚さが20~40μmである。
図2は、本発明の排ガス浄化用触媒において、上層の酸化触媒層においてHCおよびCOが選択的に酸化され、下層のNOx吸蔵還元型触媒層においてNOxが選択的に吸蔵および還元される状態を模式的に示す。
図3は、(A)実験室評価用の本発明例および従来例の触媒の構成イメージおよび(B)実機評価用の本発明例の触媒の構成イメージをそれぞれ示す模式図である。
図4は、実験室評価用の試験サイクルを示すグラフである。
図5は、本発明例および従来例の触媒について実験室でのNOx吸蔵特性を示すグラフである。
図6は、本発明例の触媒について実機でのNOx吸蔵特性を示すグラフである。
これに対して本発明の特徴として、図2に示すように、まずHC、COが上層の酸化触媒層で実質的に浄化されるため、下層のNOx吸蔵還元型触媒層の活性点をNOx吸蔵還元反応に有効利用できる。
本発明は、NOx吸蔵還元型触媒層の上に、酸化触媒層を設けたことにより、下層のNOx吸蔵還元型触媒層を有効に利用できる。すなわち、排ガスが最初に通る上層の酸化触媒層が、NOx吸蔵還元型触媒の反応を阻害するHC(炭化水素)とCO(一酸化炭素)を選択的に酸化する。したがって、下層のNOx吸蔵還元型触媒層においては、HC、CO、NOxの競争吸着が実質的に起きず、上層の酸化触媒層を通ってきたNOxの吸蔵および還元が選択的に起きる。
本発明の排ガス浄化用触媒においては、上層の酸化触媒層と下層のNOx吸蔵還元型触媒層とを選択的に作用させることにより、酸化により浄化すべきHCおよびCOと、還元により浄化すべきNOxとの競争吸着を回避し、それぞれに十分な反応サイトを確保して、NOx吸蔵還元型触媒の本来の機能を最大限に利用することができる。
一つの望ましい形態においては、図2に示したように、排ガス流の方向に対して、NOx吸蔵還元型触媒層の上流側端部から、NOx吸蔵還元型触媒層の長さの25~60%を覆うように配置する。この範囲内において、NOx吸蔵還元型触媒層のNOx吸蔵速度が最大になる。
更に、一つの望ましい形態においては、前記酸化触媒層の厚さが20~40μmである。この範囲内において、NOx吸蔵還元型触媒層のNOx吸蔵速度が最大になる。
下層のNOx吸蔵還元型触媒層を形成した後、その上から上層の酸化触媒層をオーバーコートして、上下2層コート構造の触媒を形成する。
上層にオーバーコートする酸化触媒層は、酸化性能を高めるために、酸化触媒として優れた触媒能を有するPtおよび/またはPdを備えている。
酸化触媒層には、希薄燃焼ガスでの触媒活性を妨げるRhは添加しないし、貴金属活性に影響を及ぼすNOx吸蔵材も添加しない。
NOx吸蔵還元型触媒層は、Ptおよび/またはRhとNOx吸蔵材とを含む。特に、RhもNOx吸蔵材も、下層のNOx吸蔵還元型触媒層にのみ添加する。
触媒サイズは、実験室用で容量35cc(全長50mm)、実機用で容量14L(全長110mm)である。
触媒に電気炉で700℃×27hの簡易耐久を施した。
表1のコート仕様の3種類の触媒を下記の構成で試験に供した。構成イメージを図3に示す。
<試験触媒の構成>
(A)実験室評価用の構成(3種)
[1]DOC+[2]NSR:タンデム構成(従来例)
サイズ:DOC 容量10cc、長さ14mm(上流側)
NSR 容量25cc、長さ36mm(下流側)
(全長50mm)
[2]NSR:単独(従来例)
サイズ:容量35cc、長さ(全長)50mm
[3]NSR上にDOCをオーバーコート(本発明例)
サイズ:容量35cc、長さ(全長)50mm
オーバーコート割合:27%=10cc(14mm(*))
55%=20cc(28mm(*))
82%=30cc(42mm(*))
(*)NSR上流側端部からの長さ
(B)実機評価用の構成(1種)
[3]NSR上にDOCをオーバーコート(本発明例)
サイズ:容量14L、長さ110mm
オーバーコート割合:55%=7.7L(60mm(*))
(*)NSR上流側端部からの長さ
試験条件は下記のとおりであった。
<試験条件>
(A)実験室NOx吸蔵試験
試験ガス条件:表2に示す。
すなわち、初期温度50℃から40℃/minで600℃まで昇温し、600℃でリッチスパイクNOx還元(リッチ/リーン=5sec/5sec)を行なった後、直ちにエア雰囲気で350℃まで触媒を冷却して、リーン雰囲気でNOx吸蔵を行なった。
(B)実機NOx吸蔵試験
評価エンジン:ディーゼルエンジン(排気量2.2L)
エンジン条件:表3に示す。
<試験結果>
(A)オーバーコート割合の検証
図5に、実験室NOx吸蔵試験の結果をまとめて示す。
本発明により、NSR上にDOCをオーバーコートすることにより、従来のNSR単独およびDOC/NSRタンデムに比べてNOx吸蔵速度が著しく向上した。
また、オーバーコート割合は下層のNSR長さの25%~60%の範囲でNOx吸蔵速度が最も高くなる。
(B)コート厚さの検証
図6に、実機NOx吸蔵試験の結果をまとめて示す。オーバーコート割合は55%(一定)であり、オーバーコート量を24~72g/Lの範囲で変化させた。
オーバーコート量が30g/L付近でNOx吸蔵速度は最も高くなった。最適オーバーコート量は30g/Lを中心として、25~35g/Lの範囲である。これを、オーバーコート割合55%に対して、オーバーコート厚さに換算すると、最適オーバーコート厚さは20~40μm程度である。
Claims (3)
- 基材上に、アルカリ金属またはアルカリ土類金属から選択された少なくとも1種のNOx吸蔵材と、Ptおよび/またはRhとを含むNOx吸蔵還元型触媒層を備え、
前記NOx吸蔵還元型触媒層の上に、Ptおよび/またはPdを担持した酸化触媒層を備えた
ことを特徴とする排ガス浄化用触媒。 - 請求項1において、前記酸化触媒層は、排ガス流の方向に沿って、前記NOx吸蔵還元型触媒層の上流側端部から、該NOx吸蔵還元型触媒層の長さの25~60%を覆うことを特徴とする排ガス浄化用触媒。
- 請求項1または2において、前記酸化触媒層の厚さが20~40μmであることを特徴とする排ガス浄化用触媒。
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PCT/JP2010/055774 WO2011118047A1 (ja) | 2010-03-24 | 2010-03-24 | 排ガス浄化用触媒 |
EP10848439.5A EP2551014A4 (en) | 2010-03-24 | 2010-03-24 | CATALYST FOR THE PURIFICATION OF EXHAUST GASES |
JP2012506754A JPWO2011118047A1 (ja) | 2010-03-24 | 2010-03-24 | 排ガス浄化用触媒 |
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Cited By (7)
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JP2010209905A (ja) * | 2009-03-09 | 2010-09-24 | Hyundai Motor Co Ltd | 窒素酸化物低減触媒及びこれを利用した排気装置 |
JP2013119077A (ja) * | 2011-12-08 | 2013-06-17 | Toyota Motor Corp | 排ガス浄化用触媒及びその利用 |
JP2016079913A (ja) * | 2014-10-17 | 2016-05-16 | マツダ株式会社 | 排気ガス浄化システム及び排気ガス浄化方法 |
JP2016089721A (ja) * | 2014-11-05 | 2016-05-23 | マツダ株式会社 | 排気ガス浄化システム及び排気ガス浄化方法 |
JP2016112537A (ja) * | 2014-12-17 | 2016-06-23 | トヨタ自動車株式会社 | 排ガス浄化用触媒 |
JP2017532188A (ja) * | 2014-08-12 | 2017-11-02 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | モディファイドリーンNOxトラップを有する排気システム |
JP2018009581A (ja) * | 2017-10-10 | 2018-01-18 | マツダ株式会社 | 排気ガス浄化システム及び排気ガス浄化方法 |
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JP5757297B2 (ja) * | 2013-01-23 | 2015-07-29 | トヨタ自動車株式会社 | 触媒コンバーター |
EP2956232B1 (en) | 2013-02-14 | 2017-04-05 | Haldor Topsøe A/S | Method and catalyst for the simultaneous removal of carbon monoxide and nitrogen oxides from flue or exhaust gas |
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- 2010-03-24 US US13/636,079 patent/US20130065754A1/en not_active Abandoned
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US20130065754A1 (en) | 2013-03-14 |
EP2551014A1 (en) | 2013-01-30 |
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