JP7224298B2 - 単一ブリックscr/asc/pna/doc近位連結触媒 - Google Patents
単一ブリックscr/asc/pna/doc近位連結触媒 Download PDFInfo
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- JP7224298B2 JP7224298B2 JP2019553395A JP2019553395A JP7224298B2 JP 7224298 B2 JP7224298 B2 JP 7224298B2 JP 2019553395 A JP2019553395 A JP 2019553395A JP 2019553395 A JP2019553395 A JP 2019553395A JP 7224298 B2 JP7224298 B2 JP 7224298B2
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- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific 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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
- F01N2370/04—Zeolitic material
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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
- F01N2510/063—Surface coverings for exhaust purification, e.g. catalytic reaction zeolites
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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
- 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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- 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
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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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
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Description
4NO+4NH3+O2→4N2+6H2O
2NO2+4NH3+O2→3N2+6H2O
NO+NO2+2NH3→2N2+3H2O
本発明の実施態様は、入口端及び出口端を有する基材、第1のゾーン及び第2のゾーンを含む触媒物品に関し、第1のゾーンは第2のゾーンの上流に位置する。第1のゾーンは、受動的NOx吸着体(PNA)と、担体上の白金族金属、及びSCR触媒を有するSCR層を含むアンモニアスリップ触媒(ASC)とを含むことができ、SCR層は、ASC最下層及び第1のSCR触媒より上に位置する。第2のゾーンは、ディーゼル酸化触媒(DOC)又はディーゼル発熱触媒(DEC)を含み得る。
本発明の実施態様は、第1のゾーン、第2のゾーン及び第3のゾーンを有する触媒物品に関する。第1のゾーンは、SCR触媒を含み得る。第2のゾーンは、担体上の白金族金属と第1のSCR触媒とのブレンドを有するASCを含み得る。第3のゾーンは、DOC又はDECなどの触媒(「第3のゾーン触媒」)を含み得る。触媒物品はPNAを含む。第1のゾーンは第2のゾーンの上流に位置し、第2のゾーンは第3のゾーンの上流に位置する。
本発明のシステム構成は、上流SCR触媒、及び前項に記載される2ゾーン又は3ゾーン構成を有する触媒物品であり得る。上流SCR触媒は、前項に記載される2ゾーン又は3ゾーン構成を有する触媒物品の上流に位置してもよく、いくつかの実施態様では、上流SCR触媒及び触媒物品は近位連結されてもよい。いくつかの実施態様では、上流SCR触媒及び触媒物品は単一基材上に位置しており、上流SCR触媒は、触媒物品の第1及び第2(及び存在する場合は第3)のゾーンの上流に位置する。
触媒物品は、一又は複数の、アンモニアスリップ触媒(「ASC」)とも呼ばれる、アンモニア酸化触媒を含み得る。一又は複数のASCは、SCR触媒に又はその下流に含まれて、余剰のアンモニアを酸化させ、且つそれが大気中へ放出されるのを妨げ得る。いくつかの実施態様では、ASCは、SCR触媒と同じ基材上に含まれ得るか、又はSCR触媒とブレンドされ得る。特定の実施態様では、アンモニア酸化触媒材料は、NOx又はN2Oの形成の代わりにアンモニアの酸化を有利にするよう選択され得る。好ましい触媒材料には、白金、パラジウム、又はそれらの組み合わせが含まれる。アンモニア酸化触媒は、金属酸化物に担持された白金及び/又はパラジウムを含む。いくつかの実施態様では、触媒は、高表面積の担体上に配置され、アルミナを含むが、それらに限定されない。
本発明のシステムは、一又は複数のSCR触媒を含み得る。いくつかの実施態様では、触媒物品は、第1のSCR触媒、第2のSCR触媒、及び/又は第3のSCR触媒を含み得る。いくつかの実施態様では、SCR触媒は、互いに同一の配合を含み得る。いくつかの実施態様では、SCR触媒は、互いに異なる配合を含み得る。
本発明の実施態様は、(1)担体上の白金族金属と(2)SCR触媒とのブレンドを含み得る。いくつかの実施態様では、ブレンド内で、SCR触媒の担体上の白金族金属に対する重量比は、約3:1から約300:1;約3:1から約250:1;約3:1から約200:1;約4:1から約150:1;約5:1から約100:1;約6:1から約90:1;約7:1から約80:1;約8:1から約70:1;約9:1から約60:1;約10:1から約50:1;約3:1;約4:1;約5:1;約6:1;約7:1;約8:1;約9:1;約10:1;約15:1;約20:1;約25:1;約30:1;約40:1;約50:1;約75:1;約100:1;約125:1;約150:1;約175:1;約200:1;約225:1;約250:1;約275:1;又は約300:1である。この重量比は、ブレンドがPNAを含む実施態様では、PNAからの白金族金属を含み得る。
NOx吸着体(PNA)は、金属含有モレキュラーシーブ又はセリア担持パラジウムを含む。PNAが金属含有モレキュラーシーブを含むとき、金属は、セリウム、クロム、コバルト、銅、鉄、ランタン、マンガン、モリブデン、ニッケル、ニオブ、パラジウム、タングステン、銀、バナジウム、及び亜鉛、並びにそれらの混合物からなる群より選択され得る。いくつかの実施態様では、金属は、コバルト、マンガン、パラジウム又は亜鉛である。いくつかの実施態様では、金属はパラジウム又は亜鉛である。いくつかの実施態様では、SCR触媒中の金属は銅であり、PNA中の金属はパラジウムである。PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブは、SCR触媒中のモレキュラーシーブの記載において上に記載されるようなアルミノシリケート(例えばゼオライト)、アルミノホスフェート、又はシリコアルミノホスフェートを含み得る。SCR触媒が金属含有モレキュラーシーブを含むとき、SCR触媒中の金属含有モレキュラーシーブ中のモレキュラーシーブは、PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブと同一である可能性があるか、又は、SCR触媒中の金属含有モレキュラーシーブ中のモレキュラーシーブは、PNA中の金属含有モレキュラーシーブ中のモレキュラーシーブとは異なる可能性がある。いくつかの実施態様では、同一の配合物及び/又は成分は、PNA及びSCR触媒の両方として機能し得る。
本発明の触媒物品は、SCR触媒とNOx吸着体触媒(PNA)の混合物を含み得る。いくつかの実施態様では、PNAがSCR/ASCブレンドに含まれるとき等に、混合物はASCを含み得る。
本発明の触媒物品及びシステムは、一又は複数のディーゼル酸化触媒を含み得る。酸化触媒、及び特にディーゼル酸化触媒(DOC)が、当該技術分野でよく知られている。酸化触媒は、COをCO2に酸化し、気相炭化水素(HC)及びディーゼル微粒子の有機フラクション(可溶性有機成分)をCO2とH2Oに酸化させるように設計されている。典型的な酸化触媒は、アルミナ、シリカ-アルミナ、及びゼオライトなどの高表面積の無機酸化物担体上白金及び任意選択的にパラジウムも含む。
本発明の触媒はそれぞれ、フロースルー基材又はフィルタ基材をさらに含み得る。一実施態様では、触媒は、フロースルー又はフィルタ基材上にコーティングされてもよく、好ましくは、ウォッシュコート法を使用して、フロースルー又はフィルタ基材上に堆積される。
システムは、SCR及び/又はSCRF触媒の上流の排気システムに窒素還元剤を導入するための手段を備え得る。排気システム中へ窒素還元剤を導入するための手段はSCR又はSCRF触媒のすぐ上流にある(例えば、窒素還元剤を導入するための手段とSCR又はSCRF触媒との間に介在する触媒は存在しない)ことが好ましい場合がある。
本発明の触媒物品は、PNAを含まないこと以外は一般的に同等である触媒物品と比較して、利点を含む多くの有益性を提供し得る。本発明の触媒物品は、排気システム内のEGR回路の削減又は除去を可能することができ、これは、燃費及び出力の改善、並びに炭化水素及び粒子状物質の排出の低下において有益であり得る。さらに、本発明の触媒物品は、触媒物品がエンジン後の近位連結位置に置かれているとき、SCR触媒と比較して同等又は同等に近いNO変換を提供し得る。触媒物品は、NH3下噴射中、SCR触媒と比較して、同等又は同等に近いN2O形成を提供し得る。本発明の触媒物品は、NH3上噴射中、著しく削減されたN2O形成を提供し得る。本発明の触媒物品は、尿素下噴射条件下でSCR/DOC触媒として機能すると言われることがあるが、余分なNH3が存在するとき、高いNH3選択性を有するSCR/ASC/DOCとして機能する。本発明の触媒物品は、単一ブロック中でSCR/ASC/DOC機能性を達成することができ、これは空間が限定されているときに特に望ましい。加えて、触媒物品は、エンジンの熱スウィングに対する高速応答を提供する可能性があり、これは、コールドスタート期間中のNOx変換に有益であり得る。触媒物品は、尿素噴射温度に到達する前にNOx貯蔵を提供し、追加のコールドスタートNOx制御を提供し得る。いくつかの実施態様では、触媒物品は、コールドスタート中にHC貯蔵を提供し得る。
以下の構成を用いて近位連結触媒構成を調製した:SCR/DOC、SCR-ASC/DOC及びPNA/SCR-ASC/DOC。特定の構成を図45に示す。
触媒がNOxを含有するシミュレーションされたエンジン出力ガス混合物に80℃で100秒間曝露され、その後500℃まで温度を上昇させた、シミュレーションしたNOx貯蔵-放出条件下で、上記のPNA/SCR-ASC/DOC触媒を試験した。具体的には、試験条件は以下の通りであった:200ppmのNO、500ppm(C1ベース)のC10H22、200ppmのCO、10%のO2、5%のCO2、5%のH2O、T≧180℃での300ppmのNH3噴射(あってもなくてもよい);SV=40,000h-1。触媒を、650℃/空気中10%H2O/50時間でエイジングした。
Claims (23)
- 入口端及び出口端を含む基材、第1のゾーン、第2のゾーン並びに第3のゾーンを含む触媒物品であって、
第1のゾーンが、第2のSCR触媒を含み、
第2のゾーンが、(1)担体上の白金族金属及び(2)第1のSCR触媒のブレンドを含むアンモニアスリップ触媒(ASC)を含み、
第3のゾーンが、ディーゼル酸化触媒(DOC)からなる触媒(「第3のゾーン触媒」)を含み、
第1のゾーンが第2のゾーンの上流に位置し、第2のゾーンが第3のゾーンの上流に位置しており、
触媒物品が受動的NOx吸着体(「PNA」)を含み、
ASCが第1の層に含まれており、
第3のゾーン触媒が、出口端から基材の全長未満まで延びる第2の層に含まれ、第2の層が第1の層の上に位置し、第1の層よりも長さが短く、且つ
第2のSCR触媒が、入口端から基材の全長未満まで延び、第1の層と少なくとも部分的に重なる層に含まれる、
触媒物品。 - 第1のゾーンがPNAを含む、請求項1に記載の触媒物品。
- 第2のゾーンがPNAを含む、請求項1に記載の触媒物品。
- 第1の層が出口端から基材の全長未満まで延びている、請求項1に記載の触媒物品。
- 第1の層が入口端から基材の全長未満まで延びている、請求項1に記載の触媒物品。
- 第1の層が基材の全長にわたって延びている、請求項1に記載の触媒物品。
- 第1の層が第1のゾーン及び第2のゾーンの全長を覆っている、請求項1に記載の触媒物品。
- 第1の層がPNAを更に含む、請求項1に記載の触媒物品。
- 第1の層がPNAを含むセクション(「PNAセクション」)を含み、PNAセクションがブレンドの上流に位置している、請求項8に記載の触媒物品。
- ブレンドがPNAを更に含む、請求項1に記載の触媒物品。
- 第1の層がPNA及び第3のSCR触媒を含むセクション(「PNA/SCRセクション」)を含む、請求項1に記載の触媒物品。
- 第1の層がPNA/SCRセクション及びブレンドを含み、PNA/SCR層がブレンドの上流に位置している、請求項11に記載の触媒物品。
- 第1の層がPNA/SCRセクションを含み、ブレンドがPNA/SCRセクションの上に位置している、請求項11に記載の触媒物品。
- 第1の層がブレンドを含み、PNA/SCRセクションが該ブレンドの上に位置している、請求項11に記載の触媒物品。
- 担体が、(1)シリカ、及び(2)200より高いシリカ対アルミナ比を有するゼオライトからなる群より選択されるケイ質材料を含む、請求項1に記載の触媒物品。
- 白金族金属が、白金族金属及び担体の総重量の0.5wt%から10wt%の量で担体上に存在する、請求項1に記載の触媒物品。
- ブレンド内で、第1のSCR触媒の、担体上の白金族金属に対する重量比が10:1から50:1である、請求項1に記載の触媒物品。
- 第1のSCR触媒とPNAが5:1から1:5の比で存在する、請求項1に記載の触媒物品。
- PNAがモレキュラーシーブ上の白金族金属を含む、請求項1に記載の触媒物品。
- PNAがゼオライト上のPdを含む、請求項1に記載の触媒物品。
- 窒素酸化物(NOx)、炭化水素(HC)、及び一酸化炭素(CO)を含む排気流から窒素酸化物(NOx)、炭化水素(HC)、及び一酸化炭素(CO)の排出を減少させる方法であって、
排気流を、請求項1に記載の触媒物品と接触させることを含む、
方法。 - 触媒物品に入る排気流の温度が≦180℃であるとき、排気流が≧1のアンモニア:NOxのモル比を含む、請求項21に記載の方法。
- 触媒物品に入る排気流の温度が≧180℃であるとき、排気流が>0.5のアンモニア:NOxのモル比を含む、請求項21に記載の方法。
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| PCT/US2018/025085 WO2018183639A1 (en) | 2017-03-30 | 2018-03-29 | Single brick scr/asc/pna/doc close-coupled catalyst |
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| JP6693406B2 (ja) * | 2016-12-20 | 2020-05-13 | 三菱自動車工業株式会社 | 排気ガス浄化装置 |
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| BR112019020349B1 (pt) | 2023-01-10 |
| US20190001268A1 (en) | 2019-01-03 |
| EP3600657A1 (en) | 2020-02-05 |
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| US20210162344A1 (en) | 2021-06-03 |
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| US11857925B2 (en) | 2024-01-02 |
| CN111050908A (zh) | 2020-04-21 |
| GB2566568A (en) | 2019-03-20 |
| CN111050908B (zh) | 2023-04-21 |
| RU2019134058A3 (ja) | 2021-04-30 |
| EP3600657B1 (en) | 2022-02-16 |
| GB2571640B (en) | 2021-04-14 |
| DE102018107779A1 (de) | 2018-10-04 |
| GB2571640A (en) | 2019-09-04 |
| JP2020515394A (ja) | 2020-05-28 |
| RU2019134058A (ru) | 2021-04-30 |
| RU2759670C2 (ru) | 2021-11-16 |
| BR112019020349A2 (pt) | 2020-04-28 |
| GB201805133D0 (en) | 2018-05-16 |
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