JP5552318B2 - 多孔性壁ハニカムを含むガス触媒 - Google Patents
多孔性壁ハニカムを含むガス触媒 Download PDFInfo
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Description
本願は、35U.S.C.§119(e)に基づいて、U.S.特許出願No.60/887,533(出願日、2007年1月31日)の優先権を主張する。この文献はその全てがここに導入される。
本発明の一実施の形態は、流通基材と複合触媒を含むガス処理装置であって、前記流通基材は、入口軸端、出口軸端、入口軸端から出口軸端までの間で伸びる長さを有する壁要素、及び壁要素によって規定され、軸方向に囲まれ、端部が開放されている複数の通路を有するガス処理装置に関する。ここで、壁は、多孔率性(多孔度)が少なくとも50%で、平均孔径が少なくとも5ミクロンメーター及び約100ミクロンメーター未満であり、そして壁の表面が壁の表面の開口した孔によって規定された平均粗さを有している。そして、上記複合触媒は、平均粒子径が約3ミクロンメーターを超え、実質的に壁要素内に堆積した粒子を含むワッシュコートの状態であり、壁要素の表面の平均粗さは、壁内に触媒を積載する前から実質的に変化しない。
本発明のいくつかの代表的な実施の形態を記載する前に、本発明は、以下に記載する構成又は方法(工程)の詳細に限定されないことが理解されるべきである。本発明は、他の実施の形態が可能であり、そして種々の方法で実施等をすることができる。
この技術分野では公知のように触媒成分は、通常、貴金属例えば、白金、パラジウム、ロジウム、及び/又はルテニウムを、担体に堆積した状態で含む。適切な担体は、高表面積耐火金属酸化物である。特定の実施の形態では、担体の基材の壁へのワッシュコートの積載量は、約1.4g/in3〜約7.0g/in3であり、及びより特定的には、約2.0g/in3〜約7.0g/in3の範囲である。高表面積耐火金属酸化物の例(但し、この例に限られるものではない)は、アルミナ、シリカ、チタニア、及びジルコニア及びこれらの混合物等の高表面積耐火金属酸化物を含む。高表面積耐火金属酸化物は、混合酸化物、例えば、シリカ−アルミナ、アルミノシリケート(これらは、アモルファス又は結晶質であって良い)、アルミナ−ジルコニア、アルミナ−クロミア、アルミナ−セリア及びこれらに類似するもので構成されていて良く、又は含んでいて良い。例となる耐火金属酸化物は、比表面積が約50〜約300m2/gで、約2.0〜約7.0g/in3の積載量で存在するガンマアルミナを含む。
本発明の触媒複合体は、この技術分野では公知の方法によって容易に製造される。代表的な方法を以下に説明する。
適切なSCR触媒組成は、例えば、U.S.Pat.Nos.4,961,917(’917patent)及び5,516,497に記載されており、これら両文献は、その全てがここに導入される。’917patentに開示された組成は、鉄及び銅促進剤(これらは、ゼオライト中に、促進剤とゼオライトの合計質量に対して、約0.1〜30質量%、特に約1〜5質量%の量で存在する)の少なくとも一方を含む。開示された組成物は、NOXをNH3でN2に還元可能なことに加え、これらは、過剰のNH3をO2で参加することを促進させ、特に、促進剤の濃度が高い組成物についてこの傾向が強い。
約1kgのゼオライトフィルターケーキを215gのDI水に加え、44.8%固体のスラリーを形成することにより、イオン交換したゼオライトのスラリーを製造した。連続ミルで簡単に粉砕(ミル)した後、粒子の90%が、直径8.2ミクロンメーター未満であった(レーザー回折で測定)。ジルコニアバインダーを5%ZrO2の積載量で加え、そしてスラリー固体を43.2%に調節した。
初期湿潤、及び次の酢酸での固定により、白金をアルミニウム酸化物担体(酸化アルミニウム担体)に分散させた。Ptが積載されたアルミナをスラリーとして製造し、平均粒子径が10ミクロンメーター未満になるまで粉砕し、そして多孔性(多孔度)が異なる3つのハニカムに被覆した。
空間速度=112,000hr−1(20℃、1atm)
一酸化炭素=1020ppm
プロピレン=300ppm(C1)
デカン=300ppm(C1)
水=5%
酸素=14%
二酸化炭素=4%
NO=100ppm
80℃から400℃に、10℃/分で温度傾斜
Pt及びPdをアルミニウム酸化物(酸化アルミニウム)に加え、酢酸で固定し、粉砕し、そして標準及び高多孔性ハニカムに被覆した。Pt及びPd積載は、Pt:Pd割合が4:1で、合計積載量が100g/ft3になることを目標とした。実施例12中の高多孔性ハニカムは、壁厚さが0.008インチで、360cpsiであり、そして壁の多孔性が55%であった。比較例13のハニカムは、壁厚さが0.004インチで、400cpsiであり、そして壁の多孔性が35%であった。本発明の実施の形態に従えば、高いワッシュコート積載量を達成する代わりとして、より薄い壁と組み合わされた、より高いセル密度が提案された。
デカン=133ppm(C1として)
プロパン=133ppm(C1として)
プロピレン=134ppm(C1として)
CO=1500ppm
H2O=5%
CO2=5%
O2=10%
NOとしてのNOX=100ppm
80℃から400℃に、15℃/分で温度傾斜。
12 シリンダー状外部表面
14 端部表面
14’ 接合部
16 ガス流通路
18 ガス流通路
20 隅肉部
22 被覆
Claims (14)
- 流通基材と複合触媒を含むガス処理装置であって、
前記流通基材は、入口軸端、出口軸端、入口軸端から出口軸端までの間で伸びる長さを有する壁要素、及び該壁要素によって規定され、軸方向に囲まれ、端部が開放されている複数の通路を有し、
壁部は、多孔度が少なくとも50%で、平均孔径が少なくとも5ミクロンメーター及び100ミクロンメーター未満であり、そして壁部の表面が壁部の表面の開口した孔によって規定された平均粗さを有し;及び
前記複合触媒は、平均粒子径が3ミクロンメーターを超える粒子を含み、及びワッシュコートの状態で、壁要素内に堆積し、壁要素の表面の、壁部の表面の開口した孔によって規定された前記平均粗さは、壁部内に触媒を積載する前から変化しないことを特徴とするガス処理装置。 - 孔のかなりの部分が相互に連結しており、及び壁要素を通って伸びており、そしてワッシュコートが相互に連結した孔内に配置されていることを特徴とする請求項1に記載のガス処理装置。
- 孔が、20ミクロンメーターを超える平均孔径を有し、そして壁の多孔度が70%以下であることを特徴とする請求項2に記載のガス処理装置。
- ワッシュコートの積載量が2.0g/(2.54cm)3以下では、通路には、隅肉部が存在しないことを特徴とする請求項2に記載のガス処理装置。
- ワッシュコートの積載量が2.5g/(2.54cm)3以下では、通路は、被覆の後、被覆されていない通路と比較して、断面積の損失が20%未満であることを特徴とする請求項2に記載のガス処理装置。
- ワッシュコートの積載量が7.0g/(2.54cm)3以下では、多孔度が35%未満のハニカム基材における同一の積載量のワッシュコート通路と比較して、その通路の断面積が相当に大きいことを特徴とする請求項2に記載のガス処理装置。
- ワッシュコートの少なくとも75%が、壁要素の内側に配置されていることを特徴とする請求項2に記載のガス処理装置。
- ワッシュコート内の粒子の粒子径が5〜10ミクロンメーターの範囲であることを特徴とする請求項2に記載のガス処理装置。
- ワッシュコートが、排気ガス流内のNOXを軽減するための触媒を1種以上含むことを特徴とする請求項1に記載のガス処理装置。
- 触媒が、ゼオライトとCHA構造を有する非ゼオライトアルミノシリケートを1種以上含むことを特徴とする請求項9に記載のガス処理装置。
- NOX貯蔵及び放出(NSR)触媒変換器であることを特徴とする請求項9に記載のガス処理装置。
- 選択的触媒還元(SCR)触媒であることを特徴とする請求項9に記載のガス処理装置。
- 前記触媒が、天然ゼオライト、合成ゼオライト、フォージャサイト、菱沸石、チノプチロライト、モルデン沸石、シリカライト、ゼオライトX、ゼオライトY、超安定ゼオライトY、ZSMゼオライト、オフレタイト、ベータゼオライト、USYゼオライト、ZSM−20ゼオライト、CHA構造を有するゼオライト、菱沸石及びSAPO材料の1種以上を有することを特徴とする請求項9に記載のガス処理装置。
- 触媒がV2O5を含むことを特徴とする請求項9に記載のガス処理装置。
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US88753307P | 2007-01-31 | 2007-01-31 | |
US60/887,533 | 2007-01-31 | ||
PCT/US2008/052275 WO2008094889A1 (en) | 2007-01-31 | 2008-01-29 | Gas catalysts comprising porous wall honeycombs |
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EP (1) | EP2111286B2 (ja) |
JP (1) | JP5552318B2 (ja) |
KR (2) | KR101536012B1 (ja) |
CN (1) | CN101687143B (ja) |
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AT (1) | ATE504346T1 (ja) |
BR (1) | BRPI0808159A2 (ja) |
CA (1) | CA2677107C (ja) |
DE (1) | DE602008006022D1 (ja) |
MX (1) | MX2009008206A (ja) |
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EP2111286B2 (en) | 2022-04-27 |
RU2009132612A (ru) | 2011-03-10 |
CN101687143B (zh) | 2013-01-02 |
US8318286B2 (en) | 2012-11-27 |
EP2111286B1 (en) | 2011-04-06 |
KR20150038645A (ko) | 2015-04-08 |
EP2111286A1 (en) | 2009-10-28 |
US20080317999A1 (en) | 2008-12-25 |
MY151327A (en) | 2014-05-15 |
BRPI0808159A2 (pt) | 2014-07-08 |
MX2009008206A (es) | 2009-08-28 |
ZA200905971B (en) | 2010-11-24 |
ATE504346T1 (de) | 2011-04-15 |
WO2008094889A1 (en) | 2008-08-07 |
AR065116A1 (es) | 2009-05-20 |
CA2677107C (en) | 2015-03-31 |
JP2010516466A (ja) | 2010-05-20 |
DE602008006022D1 (de) | 2011-05-19 |
KR101536012B1 (ko) | 2015-07-13 |
CN101687143A (zh) | 2010-03-31 |
CA2677107A1 (en) | 2008-08-07 |
KR20090108109A (ko) | 2009-10-14 |
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