JP5647623B2 - 一酸化炭素及び炭化水素変換のための層構造を有するディーゼル酸化触媒複合体 - Google Patents
一酸化炭素及び炭化水素変換のための層構造を有するディーゼル酸化触媒複合体 Download PDFInfo
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- JP5647623B2 JP5647623B2 JP2011546332A JP2011546332A JP5647623B2 JP 5647623 B2 JP5647623 B2 JP 5647623B2 JP 2011546332 A JP2011546332 A JP 2011546332A JP 2011546332 A JP2011546332 A JP 2011546332A JP 5647623 B2 JP5647623 B2 JP 5647623B2
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- oxidation catalyst
- palladium
- diesel oxidation
- catalyst
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- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 32
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- 238000006243 chemical reaction Methods 0.000 title description 13
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- 239000000203 mixture Substances 0.000 claims description 97
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Description
排ガスシステム、及び成分、及び支持体上のディーゼル酸化触媒材料を使用するこれらの使用方法が提供される。支持体は、ディーゼル酸化触媒(DOC)のために使用される流通設計(flow-through design)、又は触媒化煤フィルターのために使用される壁流設計であることができる。第1の局面では、ディーゼルエンジンからの排ガス放出を処理するための、層構造のディーゼル酸化触媒複合体が提供される。このディーゼル酸化触媒複合体は、ディーゼル酸化触媒材料、キャリア支持体(ここで、触媒材料は、パラジウム成分を含み、及び少なくとも2層の層を含む):
少なくとも1種の分子篩を含む炭化水素トラップ層(ここで、炭化水素トラップ層は実質的にパラジウムを有していない);
実質的に分子篩を有せず、及び実質的に酸素貯蔵成分を有しない、パラジウム成分を含むパラジウム含有層(ここで、パラジウム成分は表面積が大きい、耐火金属酸化物支持体の上に設けられている);
を含み、
触媒材料が、任意に、キャリア支持体の上及び少なくとも2層の層の下側に設けられた下側被覆層を含み;及び
触媒材料が、更に、少なくとも1種の炭化水素トラップ及び任意の下側被覆層中に設けられた酸素貯蔵成分を含む。
(i)
(a)キャリア支持体基材、
(b)少なくとも1種の酸素貯蔵化合物を含む、少なくとも1層の層(LO)、
(c)少なくとも1種の触媒的に活性なPGM成分を含む、少なくとも1層の層(LC)、
を少なくとも含む、ディーゼル酸化触媒を用意する工程、
(ii)排ガス放出物を処理するために、上記ディーゼル排ガス流を、上記ディーゼル酸化触媒と接触させる工程、
を含む方法を対象とする。
(i)
(a)キャリア支持体基材、
(b)少なくとも1種の酸素貯蔵化合物を含む、少なくとも1層の層(LO)、
(c)少なくとも1種の触媒的に活性なPGM成分を含む、少なくとも1層の層(LC)、
を少なくとも含む、触媒化煤フィルターを用意する工程、
(ii)排ガス放出物を処理するために、上記ディーゼル排ガス流を、上記触媒化された煤フィルターと接触させる工程、
を含む方法を対象とする。
触媒材料は、パラジウム成分を、5〜75g/ft3(0.18〜2.65kg/m3)の量で含む;
触媒材料は、更に、白金成分を、10g/ft3〜150g/ft3(0.35〜5.30kg/m3)の範囲出含み、白金成分の20質量%以下の量が、少なくとも1種の分子篩中に組み込まれ、及び白金成分の少なくとも80質量%の量が、パラジウム含有層の高表面積、耐火金属酸化物支持体上に存在する;
パラジウム含有層は、Pt及びPdを、0.1/1〜10/1のPt/Pd割合、又はより特定的には、1.5/1〜2.5/1のPt/Pd質量割合で含む;
酸素貯蔵成分は、ZrO2、CeO2、又は両方を含む;
酸素貯蔵成分は、Y、La、Nd、Sm、Pr及びこれらの混合物の少なくとも1種を含むOSC変性剤を含む;
15〜225g/ft3(0.53〜7.95kg/m3)の範囲の量で搭載された、合計貴金属成分;
パラジウム含有層が、キャリア支持体上に配置され、及び炭化水素トラップ層が、パラジウム含有層上に配置される;
炭化水素トラップ層が、キャリア支持体上に配置され、及びパラジウム含有層が、炭化水素トラップ層の上に配置される;
高表面積耐火金属酸化物を含む下側被覆層;
パラジウム成分を含む下側被覆層(undercoat layer);
下側被覆層と炭化水素トラップ層の両方は、独立して酸素貯蔵成分を含む;
キャリア支持体が、触媒化された煤フィルターを与える流通基材、又は壁流基材である;
パラジウム含有層が、下側被覆層の上に配置され、及び炭化水素トラップ層がパラジウム含有層の上に配置され、ここで、炭化水素トラップ層は、ベータゼオライト、ガンマアルミナ、及び白金を含む;パラジウム含有層は、更に、白金及びガンマアルミナを含み、及びPt/Pd割合が、4/1〜1/2の範囲である;及び下側被覆層が、ガンマアルミナ、及び任意にパラジウムを含む。
触媒材料は、ロジウムがフリーである。
1.1 120g/ft 3 (4237.8g/m 3 )1/1(OSCを有するPt/Pdテクノロジー):(サンプルA)
第1(底部)層のために、硝酸パラジウム溶液を0.75g/in3(0.0458g/cm3)の高多孔性γ−アルミナに加え、30g/ft3(1059g/m3)Pdを得た。得られたフリット(frit)を水と酸(例えば酢酸)中に分散させた。このスラリーに、0.75g/in3(0.0458g/cm3)のOSC材料(ZrO2:45wt%、CeO2:45wt%、La2O3:8wt%、Pr6O11:2wt%)を分散させ、そして7マイクロメーターの粒子サイズd90にミルした。最終的なスラリーをモノリス上に被覆し、110℃で乾燥させ、そして空気中で450℃でか焼した。
第1(底部)層のために、0.25g/in3(0.0153g/cm3)の高多孔性γ−アルミナ及び0.75g/in3(0.0458g/cm3)のOSC材料(ZrO2:45wt%、CeO2:45wt%、La2O3:8wt%、Pr6O11:2wt%)を水及び酸(例えば酢酸)中に分散させ、そして8マイクロメーターの粒子サイズd90にミルした。最終的なスラリーをモノリス上に被覆し、110℃で乾燥させ、そして空気中で450℃でか焼した。
第1(底部)層のために、1g/in3(0.0610g/cm3)の高多孔性γ−アルミナを水及び酸(例えば酢酸)中に分散させ、そして15マイクロメーターの粒子サイズd90にミルした。最終的なスラリーをモノリス上に被覆し、110℃で乾燥させ、そして空気中で450℃でか焼した。
試験サンプル:
2.1サンプルA:
以下の:
−第1層:30g/ft3(1059g/m3)のPd、0.75g/in3(0.0458g/cm3)のOSC、0.75g/in3(0.0458g/cm3)の高多孔性γ−アルミナ
−第2層:52g/ft3 (1836g/m 3 )のPt、30g/ft3(1059g/m3)のPd、1.5g/in3(0.0915g/cm3)の高多孔性γ−アルミナ
−第3層:8g/ft3(283g/m3)のPt、0.25g/in3(0.0153g/cm3)の高多孔性γ−アルミナ、0.5g/in3(0.0305g/cm3)のH−ベータゼオライト、0.5g/in3(0.0305g/cm3)のOSC
を含む3層触媒を試験した。
以下の:
−第1層:0.75g/in3 (0.0458g/cm 3 )のOSC、0.25g/in3 (0.0153g/cm 3 )の高多孔性γ−アルミナ
−第2層:72g/ft3 (2543g/m 3 )のPt、40g/ft3 (1413g/m 3 )のPd、1.5g/in3 (0.0915g/cm 3 )の高多孔性γ−アルミナ
−第3層:8g/ft3 (283g/m 3 )のPt、0.25g/in3 (0.0153g/cm 3 )の高多孔性γ−アルミナ、0.5g/in3 (0.0305g/cm 3 )のH−ベータゼオライト、0.5g/in3 (0.0305g/cm 3 )のOSC
を含む3層触媒を試験した。
以下の:
−第1層:1g/in3 (0.0610g/cm 3 )の高多孔性γ−アルミナ
−第2層:72g/ft3 (2543g/m 3 )のPt、40g/ft3 (1413g/m 3 )のPd、1.5g/in3 (0.0915g/cm 3 )の高多孔性γ−アルミナ
−第3層:8g/ft3 (283g/m 3 )のPt、0.25g/in3 (0.0153g/cm 3 )の高多孔性γ−アルミナ、0.5g/in3 (0.0305g/cm 3 )のH−ベータゼオライト、
を含む3層触媒を試験した。
サンプルA)、B)及びC)を、COとHC点火性能のために試験した。試験の前に、サンプルを、(2.7Lエンジン置換の)4シリンダーライトデューティーディーゼルエンジンの排ガス流れ内で25時間熟成させた。排ガス流の温度を、上流側のバーナー−DOCを使用して上昇させ、触媒を750℃の定常状態で熟成させた。
であった。温度傾斜は2℃/分であった。
Claims (15)
- ディーゼルエンジンからの排ガス放出物を処理するための層状ディーゼル酸化触媒複合体であって、
ディーゼル酸化触媒材料、キャリア支持体を含み、
この触媒材料は、パラジウム成分を含み、及び以下の層、
少なくとも1種の分子篩を含み、且つ実質的にパラジウムを含んでいない炭化水素トラップ層;
実質的に分子篩を有せず、及び実質的に酸素貯蔵成分を有せず、パラジウム成分が高表面積の耐火金属酸化物支持体の上に設けられている、パラジウム成分を含むパラジウム含有層;
を含み、
触媒材料が、任意に、キャリア支持体の上及びこれらの層の下側に設けられた下側被覆層を含み;及び
触媒材料が、更に、少なくとも1種の炭化水素トラップ層及び任意の下側被覆層中に設けられた酸素貯蔵成分を含む、
ことを特徴とする層状ディーゼル酸化触媒複合体。 - 触媒材料は、パラジウム成分を、5〜75g/ft3(0.18〜2.65kg/m3)の量で含むことを特徴とする請求項1に記載の層状ディーゼル酸化触媒複合体。
- 触媒材料が、更に、白金成分を、10g/ft3〜150g/ft3(0.35〜5.30kg/m3)の範囲で含み、白金成分の20質量%以下の量が少なくとも1つの分子篩中に組み込まれ、及び白金成分の少なくとも80質量%が、パラジウム含有層の、高表面積の耐火金属酸化物支持体の上に存在することを特徴とする請求項1又は2の何れかに記載の層状ディーゼル酸化触媒複合体。
- パラジウム−含有層が、PtとPdを、0.1/1〜10/1のPt/Pd質量割合で含むことを特徴とする請求項1〜3の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- 酸素貯蔵成分が、ZrO2、CeO2、又は両方を含むことを特徴とする請求項1〜4の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- 酸素貯蔵成分が、Y、La、Nd、Sm、Pr、及びこれらの混合物の少なくとも1種を含むOSC変性剤を含むことを特徴とする請求項5に記載の層状ディーゼル酸化触媒複合体。
- 貴金属成分の合計装填量が15〜225ft3(0.53〜7.95kg/m3)の範囲であることを特徴とする請求項1〜6の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- パラジウム含有層が、キャリア支持体の上に設けられ、及び炭化水素トラップ層がパラジウム含有層の上に設けられていることを特徴とする請求項1〜7の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- 高表面積の耐火金属酸化物を含む下側被覆層を含むことを特徴とする請求項1〜8の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- 下側被覆層を含み、及び下側被覆層と炭化水素トラップ層の両方が、独立して、酸素貯蔵成分を含むことを特徴とする請求項1〜9の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- キャリア支持体が流通基材であることを特徴とする請求項1〜10の何れか1項に記載の層状ディーゼル酸化触媒複合体。
- パラジウム含有層が下側被覆層の上に設けられ、及び炭化水素トラップ層がパラジウム含有層の上に設けられ、
炭化水素トラップ層がベータゼオライト、ガンマアルミナ、及び白金を含み;
パラジウム−含有層が、更に白金及びガンマアルミナを含み、及びPt/Pd質量割合が4/1〜1/2の範囲であり;及び
下側被覆層がガンマアルミナ、及び任意にパラジウムを含むことを特徴とする請求項1に記載の層状ディーゼル酸化触媒複合体。 - 排ガス流が、炭化水素、一酸化炭素、及び他の排ガス成分を含み、
排ガス流を、請求項1〜12の何れか1項に記載の層状ディーゼル酸化触媒複合体と接触させることを含む、ディーゼルエンジンの排ガス流を処理する方法。 - 更に、ディーゼル排ガス流を、一回以上、ディーゼル酸化触媒複合体の下流側に設けられた煤フィルター、及び触媒化煤フィルター(CSF)の上流又は下流に設けられた選択性触媒還元(SCR)触媒性物品に案内することを含む請求項13に記載の方法。
- 炭化水素、一酸化炭素、及び他の排ガス成分を含むディーゼルエンジン排ガス流を処理するためのシステムであって、
ディーゼルエンジンと排ガスマニホルドを介して流体連結している排ガス導管;
前記キャリア支持体が、流通基材又は壁流基材である、請求項1〜12の何れか1項に記載のディーゼル酸化触媒複合体;及び
複合体と流体的に連結している、以下の:煤フィルター、選択的触媒還元(SCR)触媒物品、及びNOx貯蔵及び還元(NSR)触媒物品の1つ以上、
を含むシステム。
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US14536709P | 2009-01-16 | 2009-01-16 | |
US61/145,367 | 2009-01-16 | ||
US12/686,817 US8211392B2 (en) | 2009-01-16 | 2010-01-13 | Diesel oxidation catalyst composite with layer structure for carbon monoxide and hydrocarbon conversion |
US12/686,817 | 2010-01-13 | ||
PCT/US2010/021048 WO2010083313A2 (en) | 2009-01-16 | 2010-01-14 | Diesel oxidation catalyst composite with layer structure for carbon monoxide and hydrocarbon conversion |
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CN102355950B (zh) | 2015-02-25 |
EP2387460A2 (en) | 2011-11-23 |
BRPI1007341A2 (pt) | 2017-11-21 |
WO2010083313A3 (en) | 2010-12-02 |
EP2387460A4 (en) | 2012-09-12 |
US20100180581A1 (en) | 2010-07-22 |
WO2010083313A2 (en) | 2010-07-22 |
US8211392B2 (en) | 2012-07-03 |
KR101747445B1 (ko) | 2017-06-14 |
BRPI1007341B8 (pt) | 2020-03-03 |
KR20110126622A (ko) | 2011-11-23 |
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