JP2017516643A - Nox吸着剤活性を有するディーゼル酸化触媒 - Google Patents
Nox吸着剤活性を有するディーゼル酸化触媒 Download PDFInfo
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- JP2017516643A JP2017516643A JP2016560508A JP2016560508A JP2017516643A JP 2017516643 A JP2017516643 A JP 2017516643A JP 2016560508 A JP2016560508 A JP 2016560508A JP 2016560508 A JP2016560508 A JP 2016560508A JP 2017516643 A JP2017516643 A JP 2017516643A
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- Prior art keywords
- washcoat
- oxidation catalyst
- zeolite
- substrate
- area
- Prior art date
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- Granted
Links
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 165
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Images
Classifications
-
- 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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
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Abstract
Description
(a)第1のウォッシュコート領域上に配置又は担持されうる(例えば図2から4参照);及び/又は
(b)基材上に直接配置 されうる[すなわち第2のウォッシュコート領域は基材の表面と接触している](例えば図1から3参照);及び/又は
(c)第1のウォッシュコート領域と接触しうる[すなわち第2のウォッシュコート領域は第1のウォッシュコート領域に隣接又は当接している]。
(i)第2のウォッシュコート領域上に配置又は担持されうる(例えば図2、3及び5参照);及び/又は
(ii)基材上に直接配置されうる[すなわち第1のウォッシュコート領域は基材の表面と接触している](例えば図1から3参照);及び/又は
(iii)第2のウォッシュコート領域と接触しうる[すなわち第1のウォッシュコート領域は第2のウォッシュコート領域に隣接又は当接している]。
(i)PGMが(a)白金又は(b)白金及びパラジウムのいずれかであり、かつ、第3のウォッシュコート領域がパラジウムの全重量以上の白金の全重量を含む(例えばPt:Pdの重量比は≧1:1である)場合;及び/又は
(ii)PGMのための担体材料がドーパントをドープされたアルミナ、とりわけケイ素をドープされたアルミナである場合。
(i)PGMが(a)白金又は(b)白金及びパラジウムのいずれかであり、かつ、第3のウォッシュコート領域がパラジウムの全重量以上の白金の全重量を含む(例えばPt:Pdの重量比は≧1:1である)場合;及び/又は
(ii)PGMのための担体材料が任意選択的にドーパントでドープされたアルミナ、例えば任意選択的にケイ素をドープされたアルミナである場合。
(a)第3のウォッシュコート領域上に配置又は担持されうる;及び/又は
(b)基材上に直接配置されうる[すなわち第2のウォッシュコート領域は基材の表面と接触する];及び/又は
(c)第3のウォッシュコート領域と接触されうる[すなわち第2のウォッシュコート領域は第1のウォッシュコート領域に隣接又は当接する]。
(a)第3のウォッシュコート領域上に配置又は担持されうる;及び/又は
(b)基材上に直接配置されうる[すなわち第1のウォッシュコート領域は基材の表面と接触する];及び/又は
(c)第3のウォッシュコート領域と接触されうる[すなわち第1のウォッシュコート領域は、第1のウォッシュコート領域に隣接又は当接する]。
「ウォッシュコート」という用語は、当該技術分野ではよく知られており、通常は触媒の製造の間に、基材に塗布される接着性コーティングを指す。
(a)基材の入口チャネルの閉塞端(例えばブロック端又は塞栓端)に対するよりも、基材の入口チャネルの入口端(例えば開放端)に近いウォッシュコート区域、及び/又は
(b)基材の出口チャネルの出口端(例えば開放端)に対するよりも、基材の出口チャネルの閉塞端(例えばブロック端又は塞栓端)に近いウォッシュコート区域。
(a)基材の出口チャネルの閉塞端(例えばブロックされた又は塞栓された)に対するよりも、基材の出口チャネルの出口端(例えば開放端)に近いウォッシュコート区域、及び/又は
(b)基材の入口チャネルの入口端(例えば開放端)に対するよりも、基材の入口チャネルの閉塞端(例えばブロック端又は塞栓端)に近いウォッシュコート区域。
CHA構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。確立されたコーティング技術を用いて、構造1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含むコーティングが得られた。このコーティングのPdローディングは80g ft−3であった。
硝酸PdをMFI構造を有する中細孔ゼオライトのスラリーに加え、攪拌した。確立されたコーティング技術を用いて、構造1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは80g ft−3であった。
触媒実施例1及び2を、10%水中、750℃で16時間、水熱劣化させた。1.6リットルのベンチを取り付けたディーゼルエンジンを使用して、模擬的MVEG−B排出サイクルについてこれらの性能を試験した。排出は、触媒の前後に測定した。蓄積されたNOx汚染物質排出を図6に示す。エンジンアウト(触媒前)のNOx排出と触媒後のNOx排出との差異は、触媒上に貯蔵されたNOxの量を示している。貯蔵されたNOxの量は、800から850秒の間に最大に達している。排気ガス温度は850秒後に上昇し、エンジンアウトと触媒後のNOxの差異は低下する。この温度領域では、NOxは触媒から熱的に放出されている。小細孔のCHA構造化ゼオライトを含む実施例1は、中細孔のMFI構造化ゼオライトを含む実施例2よりもNOxを貯蔵する能力が大きい。
CHA構造を有する小細孔ゼオライトのスラリーに硝酸Pdを加え、攪拌した。確立されたコーティング技術を用いて、構造1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスにスラリーを塗布した。コーティングを乾燥させ、500℃で焼成した。Pd交換ゼオライトを含有するコーティングが得られた。このコーティングのPdローディングは60g ft−3であった。
硝酸パラジウムを、水中、セリアのスラリーに加えた。硝酸パラジウムを含有するスラリーを攪拌して均質化し、次いで、確立されたコーティング技術を用いて、構造1平方インチ当たり400セルを有するコーディエライトフロースルーモノリスに塗布した。コーティングを乾燥させて500℃で焼成した。このコーティングのPdローディングは60g ft−3であった。
NO酸化の測定
触媒実施例3及び4からコア試料を採取した。両コアを、炉内において800℃で16時間、10%水中で水熱劣化させた。
Claims (28)
- ディーゼルエンジンからの排気ガスを処理するための酸化触媒であって、
貴金属とゼオライトを含有するゼオライト触媒を含む、NOxを吸着するための第1のウォッシュコート領域;
白金(Pt)及び担体材料を含む、一酸化窒素(NO)を酸化するための第2のウォッシュコート領域;及び
入口端及び出口端を有する基材を備える、酸化触媒。 - 貴金属が、パラジウム(Pd)、白金(Pt)、ロジウム(Rh)、金(Au)、銀(Ag)、イリジウム(Ir)、ルテニウム(Ru)、オスミウム(Os)及びこれらの2種類以上の混合物からなる群より選択される、請求項1に記載の酸化触媒。
- ゼオライト触媒が、ゼオライトの細孔の内側に位置する少なくとも1重量%の貴金属を有する、請求項1又は2に記載の酸化触媒。
- ゼオライトが、小細孔ゼオライト、中細孔ゼオライト及び大細孔ゼオライトから選択される、請求項1から3のいずれか一項に記載の酸化触媒。
- ゼオライトが、ACO、AEI、AEN、AFN、AFT、AFX、ANA、APC、APD、ATT、CDO、CHA、DDR、DFT、EAB、EDI、EPI、ERI、GIS、GOO、IHW、ITE、ITW、LEV、KFI、MER、MON、NSI、OWE、PAU、PHI、RHO、RTH、SAT、SAV、SIV、THO、TSC、UEI、UFI、VNI、YUG、ZON及びこれらのいずれか2つ以上の混合又は連晶からなる群より選択されるフレームワークタイプを有する小細孔ゼオライトである、請求項1から4のいずれか一項に記載の酸化触媒。
- 小細孔ゼオライトがAEI又はCHAのフレームワークタイプを有する、請求項5に記載の酸化触媒。
- ゼオライト触媒が、鉄(Fe)、銅(Cu)、マンガン(Mn)、クロム(Cr)、コバルト(Co)、ニッケル(Ni)、スズ(Sn)及びこれらの2種類以上の混合物からなる群より選択される卑金属をさらに含む、請求項1から6のいずれか一項に記載の酸化触媒。
- ゼオライト触媒が、鉄(Fe)、銅(Cu)、マンガン(Mn)、クロム(Cr)、コバルト(Co)、ニッケル(Ni)、スズ(Sn)及びこれらの2種類以上の混合物からなる群より選択される卑金属などの卑金属を実質的に含まない、請求項1から6のいずれか一項に記載の酸化触媒。
- ゼオライトが10から200のシリカのアルミナに対するモル比を有する、請求項1から8のいずれか一項に記載の酸化触媒。
- 第2のウォッシュコート領域が白金(Pt)を唯一の白金族金属として含む、請求項1から9のいずれか一項に記載の酸化触媒。
- 担体材料が、アルミナ、シリカ、チタニア、ジルコニア、セリア及びこれらの2種類以上の混合又は複合酸化物からなる群より選択される耐火性金属酸化物を含有する、請求項1から10のいずれか一項に記載の酸化触媒。
- 担体材料がドーパントをドープされたアルミナを含有する、請求項11に記載の酸化触媒。
- 担体材料がシリカをドープされたアルミナを含有する、請求項12に記載の酸化触媒。
- 第2のウォッシュコート領域がアルカリ土類金属をさらに含有する、請求項1から13のいずれか一項に記載の酸化触媒。
- 第2のウォッシュコート領域がマンガンをさらに含有する、請求項1から13のいずれか一項に記載の酸化触媒。
- 第1のウォッシュコート領域が、基材の出口端で、かつ排気ガスが第2のウォッシュコート領域に接触した後に、排気ガスと接触するように配置される、請求項1から15のいずれか一項に記載の酸化触媒。
- 第1のウォッシュコート領域が基材の出口端に配置された第1のウォッシュコート区域であり、第2のウォッシュコート領域が基材の入口端に配置された第2のウォッシュコート区域である、請求項16に記載の酸化触媒。
- 第2のウォッシュコート領域が第2のウォッシュコート層であり、第1のウォッシュコート領域が第1のウォッシュコート区域であり、第1のウォッシュコート区域が基材の出口端において第2のウォッシュコート層上に配置される、請求項16に記載の酸化触媒。
- 第2のウォッシュコート領域が第2のウォッシュコート層であり、第1のウォッシュコート領域が第1のウォッシュコート層であり、第2のウォッシュコート層が第1のウォッシュコート層上に配置される、請求項16に記載の酸化触媒。
- 第2のウォッシュコート領域が、基材の出口端又はその近くで、かつ排気ガスが第1のウォッシュコート領域と接触した後に、排気ガスと接触するように配置される、請求項1から15のいずれか一項に記載の酸化触媒。
- 第2のウォッシュコート領域が基材の出口端に配置された第2のウォッシュコート区域であり、第1のウォッシュコート領域が基材の入口端に配置された第1のウォッシュコート区域である、請求項20に記載の酸化触媒。
- 第1のウォッシュコート領域が第1のウォッシュコート層であり、第2のウォッシュコート領域が第2のウォッシュコート区域であり、第2のウォッシュコート区域が基材の出口端において第1のウォッシュコート層上に配置される、請求項20に記載の酸化触媒。
- 第1のウォッシュコート領域が第1のウォッシュコート層であり、第2のウォッシュコート領域が第2のウォッシュコート層であり、第2のウォッシュコート層が第1のウォッシュコート層上に配置される、請求項20に記載の酸化触媒。
- 基材がスルーフロー基材である、請求項1から23のいずれか一項に記載の酸化触媒。
- 請求項1から24のいずれか一項に記載の酸化触媒と排出制御装置とを備える排気システム。
- 排出制御装置が、リーンNOxトラップ(LNT)、アンモニアスリップ触媒(ASC)、ディーゼル微粒子フィルター(DPF)、選択的触媒還元(SCR)触媒、触媒化スートフィルター(CSF)、選択的触媒還元フィルター(SCRFTM)触媒、及びこれらの2つ以上の組み合わせからなる群より選択される排出制御装置からなる群より選択される、請求項25に記載の排気システム。
- ディーゼルエンジン、及び、請求項1から24のいずれか一項に記載の酸化触媒又は請求項25又は26に記載の排気システムを備える車両又は装置。
- ディーゼルエンジンからの排気ガスを処理する方法であって、排気ガスを請求項1から24のいずれか一項に記載の酸化触媒に接触させること、又は、排気ガスを請求項25又は26に記載の排気システムに通過させることを含む方法。
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GBGB1501119.0A GB201501119D0 (en) | 2014-04-01 | 2015-01-23 | Diesel oxidation catalyst with NOx adsorber activity |
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PCT/GB2015/051015 WO2015150805A1 (en) | 2014-04-01 | 2015-04-01 | DIESEL OXIDATION CATALYST WITH NOx ADSORBER ACTIVITY |
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BR112016022331B1 (pt) | 2021-11-23 |
GB2536582B (en) | 2018-12-26 |
GB2524903B (en) | 2018-12-12 |
WO2015150805A1 (en) | 2015-10-08 |
EP3593894B1 (en) | 2022-11-23 |
EP3597287A1 (en) | 2020-01-22 |
CN112316973A (zh) | 2021-02-05 |
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GB2524903A (en) | 2015-10-07 |
EP3597287B1 (en) | 2023-06-21 |
DE102015105029A1 (de) | 2015-10-01 |
RU2016142583A3 (ja) | 2018-05-10 |
KR102366049B1 (ko) | 2022-02-23 |
US20150273452A1 (en) | 2015-10-01 |
GB201501119D0 (en) | 2015-03-11 |
KR20160140878A (ko) | 2016-12-07 |
GB201505617D0 (en) | 2015-05-13 |
JP6767874B2 (ja) | 2020-10-14 |
GB201405868D0 (en) | 2014-05-14 |
GB201608668D0 (en) | 2016-06-29 |
BR112016022331A2 (pt) | 2017-08-15 |
RU2016142583A (ru) | 2018-05-10 |
GB2536582A (en) | 2016-09-21 |
EP3126035B1 (en) | 2019-10-16 |
CN106163641A (zh) | 2016-11-23 |
EP3126035A1 (en) | 2017-02-08 |
RU2704801C2 (ru) | 2019-10-31 |
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