JP2016513584A - ディーゼル用途のための区域指定触媒 - Google Patents
ディーゼル用途のための区域指定触媒 Download PDFInfo
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- JP2016513584A JP2016513584A JP2016502080A JP2016502080A JP2016513584A JP 2016513584 A JP2016513584 A JP 2016513584A JP 2016502080 A JP2016502080 A JP 2016502080A JP 2016502080 A JP2016502080 A JP 2016502080A JP 2016513584 A JP2016513584 A JP 2016513584A
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- Prior art keywords
- washcoat
- area
- zone
- oxidation catalyst
- substrate
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- 229910052712 strontium Inorganic materials 0.000 description 1
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Abstract
Description
用語「基体」は、通常触媒種をその上部に有する複数の担体を含む捨て塗り形態の耐火性金属酸化物担体がその上部に配置される、単一塊材料を指す。1つ以上の実施形態によれば、基体は、DOC触媒を調製するのに通常用いられるそれらの材料のうちのいずれかである場合があり、好ましくは金属またはセラミック蜂巣構造を含むことになる。通路は流体の流れを通すように開けられ、基体の吸入面または吐出面から貫通して延びる複数の細かい平行なガス流路を有する種類の単一塊基体のような、いずれかの適切な基体が用いられ得る。それらの流体吸入口から流体吐出口までの本質的に直線経路である通路は、触媒材料が「捨て塗り」として被覆される壁により定義されるので、通路を貫流するガスは、触媒材料に接触する。捨て塗りは、液体溶媒中に担体の特定の固体含有量(例えば、重量で30〜50%)を含むスラリーを準備し、次に捨て塗り層を与えるためにそのスラリーを基体上に被覆し、乾燥させることにより形成される。
1つ以上の実施形態による触媒複合物は、単一層内にまたは多重層内に形成され得る。ある状況では、触媒金属の1つのスラリーを調製し、基体上に多重層を形成するようにこのスラリーを用いるのが適している場合がある。周知のプロセス、例えば初期湿潤により触媒複合物を調製することができる。代表的なプロセスが、以下に説明される。用語「捨て塗り」は、本明細書で用いられる場合、その通常の、処理されるガス流が貫流し得るのに十分に多孔質である蜂巣型基体部材のような基体基体材料に付与される触媒性または他の材料の粘着薄膜を意味する。
4NH3+4NO+O2→4N2+6H2O
(2)「高速」:
4NH3+2NO+2NO2→4N2+6H2O
(3)「低速」
4NH3+3NO2→3.5N2+6H2O
董青石蜂巣状単一塊基体上にPt及びPd含有水系スラリーを被覆することにより、50/50混合の擬似ベーマイトアルミナ担体及び4%酸化ランタン安定化アルミナ担体の担体上にPt及びPdを均一に混合することで捨て塗りPt/Pd組成物を調製した。総貴金属充填量は40g/ft3であり、Pt/Pd比は10:1であった。Pt及びPd含有水系スラリーは以下のように調製した。
上の比較例2と同じ方法で、40g/ft3の吸入区域貴金属充填量と2:1のPt/Pd比で捨て塗りPt/Pd組成物を調製した。背面区域は20g/ft3のPGM充填量を有し、Pt/Pd比は10:1であった。
担体粒子が、D9018〜20ミクロンの粒径に粉砕された大径細孔容積(120オングストロームの平均孔径)を有する純粋なアルミナであったことを除き、実施例3と同様の方法で捨て塗りを作製し、塗布した。
吸入区域が1:1のPt/Pd比を有したことを除き、実施例4と同様に触媒製品を調製した。充填量は吸入区域と吐出区域とで同じであって、吐出区域内のPt/Pd比は10:1であった。
吸入区域が全てPdであった(Pt:Pd=0:1)ことを除き、実施例5で記載されたのと同じ手続に従って、この実施例で記載される区域指定触媒を調製した。
吐出捨て塗り区域が3:1のPt/Pd比を含み、担体が大径細孔容積を有するシリカ・アルミナ(5%シリカ)であったことを除き、実施例5で記述されたのと同じ手続に従って、この実施例で記載される区域指定触媒を調製した。
吐出捨て塗り区域がPt/Pdを5:1の比率で含んでいたことを除き、実施例7に対して記載されたのと同じ手続に従って、この実施例で記載される区域触媒を調製した。
吐出捨て塗り区域がPt/Pdを10:1の比率で含んでいたことを除き、実施例7に対して記載されたのと同じ手続に従って、この実施例で記載される区域触媒を調製した。
吐出捨て塗り区域が全てPt(Pt:Pd=1:0)を含んでいたことを除き、実施例7に対して記載されたのと同じ手続に従って、この実施例で記載される区域触媒を調製した。
実施例11は、上の比較例2に類似し、吸入区域及び吐出区域が長さで等しい、300cpsiで10.5インチD×6インチLの全寸蜂巣状基体を含んでいた。総PGM充填量は10:1であって、吸入区域は60g/ft3のPGMを有し、吐出区域は20g/ft3の背面PGM充填量を有した。
担体粒子が、D9018〜20ミクロンの粒径に粉砕された大径細孔容積(120オングストロームの平均孔径)を有する純粋なアルミナ担体であったことを除く、実施例11と同様の実施例12を準備した。総PGM充填量は40g/ft3であった。吸入区域は基体の全長の33%であり、吐出区域は全長の67%であった。吸入区域PGM充填量は1:2のPt/Pd比で57.5g/ft3であり、吐出区域PGM充填量は10:1のPt/Pd比で20g/ft3であった。
実施例13は、担体粒子が、6ミクロンの粒径D50を有する〜5%のシリカ−アルミナであったことを除き、実施例12と同様とした。
実施例14は、下塗りがなかったことを除き、実施例13と同様とした。
試料検査
実施例1〜10を、300CPSI/5ミルの蜂巣状基体中核試料について1インチD×3インチLの中核試料で検査した。擬似苛酷ディーゼル条件下において検査室用反応器内で実施例1〜10からの試料を検査した。試料の各々を700℃で5時間にわたり空気及び10%水蒸気中で劣化させた。空間速度は100,000/時間であった。ガス組成は8%のO2であり、残りはN2であった。燃料着火を検査するために300℃から始まり次に275℃及び250℃の範囲内で擬似排気ガスを保持した。活性再生サイクルを擬似するためにディーゼル燃料をガス流内に注入した。吸入ガス温度が低くなるにつれて注入率が増加した。DOCを出るガスの目標温度は600℃であった。
実施例1〜10から選択された中核試料を以下の条件下でNO酸化に対しても検査した。ガス組成は、50,000/時間の空間速度でCOが500ppm、総HCが400ppm、O2が10%、NOが300ppm、CO2が5%及びH2Oが5%であった。
実施例11〜14で調製された被覆触媒組成物を以下のように検査した。ディーゼル検査エンジンの排気流内に第1の被覆単一塊を備え付け、次に高温注入後劣化試験に曝した。触媒の吸入(前)面での温度を400℃で維持し、次に触媒の前の排気ガス流内に燃料を周期的に注入することによりこれを達成した。注入燃料は触媒内を通り、燃焼され、それにより触媒の吐出(背)面で測定された温度が上昇した。排気流内に注入される燃料の量を制御することにより触媒の吐出(背)面で測定された温度を制御した。この方法を用いて、触媒の背面での温度は50時間にわたり650℃であった。触媒が一様な燃料燃焼に有効である最低温度を定めるために燃料燃焼能力をさまざまな温度と空間速度で検査した。実行中、DOCからのNOxを測定した。
Claims (15)
- ディーゼルエンジンからの排気ガス排出を削減するための酸化触媒複合物であって、
長さ、吸入端及び吐出端、担体上の触媒材料を有する基体を備え、前記触媒材料は第1のウォッシュコート区域と第2のウォッシュコート区域とを含んでおり、
前記第1のウォッシュコート区域は、白金Pt及びパラジウムPd白金族金属(PGM)成分を含む第1のウォッシュコート層と第1の耐火性金属酸化物担体とを備え、前記第1のウォッシュコート区域は、前記基体の前記吸入端に隣接しており、
前記第2のウォッシュコート区域は、白金及びパラジウムPGM成分を含む第2のウォッシュコート層と第2の耐火性金属酸化物担体とを備え、前記第2のウォッシュコート層は、前記基体の前記吐出端に隣接しており、
前記第1のウォッシュコート区域は、前記第2のウォッシュコート区域よりも短い長さを有し、前記酸化触媒は、前記触媒の前記吸入面上で高いPGM充填量を含まず、前記第1のウォッシュコート区域は、前記第2のウォッシュコート区域の充填量の少なくとも2倍のPGM充填量を有し、前記第1のウォッシュコート区域は、3:1未満のPt/Pd比を有する、前記酸化触媒複合物。 - 前記第2のウォッシュコート区域が、3:1超過のPt:Pd比を有する、請求項1に記載の酸化触媒複合物。
- 前記第2のウォッシュコート区域内の前記Pt:Pd比が5:1よりも大きい、請求項1または2に記載の酸化触媒複合物。
- 前記第2のウォッシュコート区域内の前記Pt:Pd比が8:1よりも大きい、請求項1〜3のいずれか1項に記載の酸化触媒複合物。
- 前記耐火性金属酸化物担体が大径細孔アルミナを含む、請求項1〜4のいずれか1項に記載の酸化触媒複合物。
- 前記アルミナがドーピングにより安定化されている、請求項5に記載の酸化触媒複合物。
- 前記ウォッシュコート充填量が、前記第1のウォッシュコート区域と前記第2のウォッシュコート区域とで同じである、請求項1〜6のいずれか1項に記載の酸化触媒複合物。
- 前記ウォッシュコート充填量が、前記第1のウォッシュコート区域と前記第2のウォッシュコート区域とで異なる、請求項1〜6のいずれか1項に記載の酸化触媒複合物。
- 前記第1のウォッシュコート区域が、約40g/ft3〜60g/ft3の範囲の量のPt/Pd成分を含む、請求項1〜8のいずれか1項に記載の酸化触媒複合物。
- 前記第2のウォッシュコート区域が、約15g/ft3〜25g/ft3の範囲の量のPd/Pd成分を含む、請求項1〜9のいずれか1項に記載の酸化触媒複合物。
- 前記第1のウォッシュコート区域が、約60g/ft3〜70g/ft3の範囲の量のアルカリ土類金属をさらに含む、請求項9に記載の酸化触媒複合物。
- 前記第1のウォッシュコート区域の前記長さに対する前記第2のウォッシュコート区域の前記長さの前記比率が1.5:1以上である、請求項1〜11のいずれか1項に記載の酸化触媒。
- ディーゼル排気ガス流を処理するための方法であって、前記排気ガス流を吸入端に通して触媒煤煙フィルタの吐出端に向けることを含み、前記排気ガスが初めに、白金Pt及びパラジウムPd成分を含む第1のウォッシュコート層と第1の耐火性金属酸化物担体とを含む前記触媒煤煙フィルタ上の第1のウォッシュコート区域を貫流し、前記方法が次に、白金及びパラジウム成分を含む第2のウォッシュコート層と第2の耐火性金属酸化物担体とを含む前記触媒煤煙フィルタ上の第2のウォッシュコート区域に前記排気ガス流を通すことを含み、前記第1のウォッシュコート区域は、前記第2のウォッシュコート区域よりも短い長さを有し、前記第1のウォッシュコート区域は、前記第2のウォッシュコート区域の充填量の少なくとも2倍のPGM充填量を有し、前記第1のウォッシュコート区域は、3:1未満のPt/Pd比を有する、方法。
- 炭化水素類、一酸化炭素、及び他の排気成分を含む希薄燃焼エンジン排気ガス流を処理するためのシステムであって、前記排出処理システムは、
排気多岐管を介して前記希薄燃焼エンジンと流体的に連通する排気管と、
請求項1〜12のいずれか1項に記載の前記酸化触媒複合物であって、前記基体がフロースルー基体または壁面流基体である、酸化触媒複合物と、
前記酸化触媒複合物から下流に配置される触媒煤煙フィルタ及びSCR触媒と、を含む、前記システム。 - 前記SCR触媒が前記触媒煤煙フィルタ上に充填される、請求項14に記載のシステム。
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- 2014-03-13 BR BR112015022281-1A patent/BR112015022281B1/pt active IP Right Grant
- 2014-03-13 EP EP14716707.6A patent/EP2969205B1/en active Active
- 2014-03-13 MX MX2015011410A patent/MX2015011410A/es unknown
- 2014-03-13 WO PCT/US2014/026230 patent/WO2014151677A1/en active Application Filing
- 2014-03-13 CN CN201480014031.0A patent/CN105188930B/zh active Active
- 2014-03-13 KR KR1020157024710A patent/KR102251564B1/ko active IP Right Grant
- 2014-03-13 PL PL14716707.6T patent/PL2969205T3/pl unknown
- 2014-03-13 CA CA2898327A patent/CA2898327A1/en not_active Abandoned
- 2014-03-13 RU RU2015143688A patent/RU2015143688A/ru not_active Application Discontinuation
- 2014-03-13 JP JP2016502080A patent/JP6727119B2/ja active Active
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Also Published As
Publication number | Publication date |
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WO2014151677A1 (en) | 2014-09-25 |
JP6727119B2 (ja) | 2020-07-22 |
US9333490B2 (en) | 2016-05-10 |
PL2969205T3 (pl) | 2023-03-20 |
KR20150131029A (ko) | 2015-11-24 |
MX2015011410A (es) | 2016-04-20 |
CN105188930A (zh) | 2015-12-23 |
CA2898327A1 (en) | 2014-09-25 |
EP2969205B1 (en) | 2023-01-18 |
US20140271429A1 (en) | 2014-09-18 |
EP2969205A1 (en) | 2016-01-20 |
BR112015022281B1 (pt) | 2021-02-09 |
CN105188930B (zh) | 2018-04-03 |
RU2015143688A (ru) | 2017-04-18 |
JP7218995B2 (ja) | 2023-02-07 |
JP2020104112A (ja) | 2020-07-09 |
BR112015022281A2 (pt) | 2017-07-18 |
KR102251564B1 (ko) | 2021-05-13 |
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