JP2012518734A - ディーゼルエンジンからの排ガスを浄化する方法 - Google Patents
ディーゼルエンジンからの排ガスを浄化する方法 Download PDFInfo
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Abstract
Description
接触酸化であり、その際、
CO、NO及びHCがO2と反応してCO2、NO2及びH2O及び熱が生ずる;
選択的接触還元であり、その際、
NO及びNO2が、NH3により典型的に還元されてN2及びH2Oが生成される;及び
触媒的に被覆されたフィルターでの粒子の捕獲であり、その際、
CO、C、HC及び生じ得るNH3のスリップ(slip)がN2、CO2及びH2Oへと酸化される。
(1) エンジン → DOC→cDPF → Ureainj → zSCR
ここで、DOCはNO2を形成するためのPtを含むディーゼル酸化触媒であり、そしてcDPFは、これもまたNO2を形成するためのPtを含む触媒化煤フィルターである。
(2) エンジン → HCinj → DOC→ cDPF → zSCR
ここで、HCinjは炭化水素であり、これはエンジンからの排ガス中及びDOCの上流へ注入される。
(3) エンジン → DOC → Ureainj → zSCR → cDPF
ここで、zSCRはゼオライトベースのSCR触媒又は機能化酸性卑金属酸化物混合物触媒であり、最低750℃の耐性を有する。
(4) エンジン → HCinj → DOC → zSCR → cDPF Tfilterin = 620℃、10分間
工程(3)は、現在の技術に比べて多くの利点を有しているが、二酸化窒素による受動的なフィルターの再生の間に一つの欠点を有すると思われる。本発明は、公知技術工程(1)において示されるような、触媒化フィルター下流のSCR触媒による系に比べてSCR下流における非常に低いNO2濃度の系(3)のこの見かけ上の欠点を解決するものである。本発明は、NO2を用いる煤フィルターの受動的な再生を確保する。
(5) エンジン → DOC → zSCR → cDPF
(6) エンジン (noEGR) → DOC → zSCR → cDPF
(7) エンジン → NH3inj → DOC → zSCR → cDPF
(8) エンジン(noEGR) → NH3inj → DOC → zSCR → cDPF
系(3)は、ディーゼル後注入を用いる乗用車に関して、特に興味深いものである。
(9) エンジン → DOC(1) → Ureainj → SCR → HCinj → DOC(2) → cDPF.
(10) エンジン → DOC (1) → NH3inj → zSCR → HCinj → DOC(2) → cDPF
そして、低温始動時及び同時能動的再生は次の通りである。
(11) Engine→ NH3inj → DOC (1)→NH3inj →zSCR→ HCinj→ DOC(2)→ cDPF
(12) エンジン → Ureainj → V−SCR → HCinj→ DOC→ cDPF
銅ベースゼオライトSCR触媒、Cu−zSCRは、NO2/NO比にほとんど依存しないが、エンジンからのHC放出に耐えることから、選択されたSCR触媒として使用できる。
(13) エンジン → NH3inj →V−SCR → HCinj→ DOC→ cDPF
系(13)では、エンジンマニホールドからV−SCR触媒までの距離を、因数10で50cmから5cmまで減少させることができる。それ故、低温始動時のエンジンの熱は、余分な管長を加熱するのに使用されるのではなく、化学反応を開始させるのに使用される。系(13)は、NH3注入が停止される管理された受動的な再生の間、一時的に次の通りである。
(14) エンジン → V−SCR → DOC → cDPF
そして、EGRのない場合と同等であるのが次である。
(15) エンジン (noEGR) → V−SCR→ DOC → cDPF
系(12)は、トラック用途に特に関心が持たれている。
SCR+DOC+cDPF系を用いたスカニア(Scania)12リットルエンジンに対するエンジンベンチテストにより、断続的な尿素の計量添加及び一時的な高NO2含有量での、7回の世界統一試験サイクル(world harmonized test cycles)後の、変化していない煤添加(スートロード(soot load))圧力降下が与えられる。
図5において、二つの曲線は同じであり、従って、これら曲線はそれぞれ最高の状態で書かれている。これは、追加的な煤添加によって圧力降下が増大しないことを示していることを意味する。この結果は、以下の参照例と比較すべきである。
Claims (14)
- 選択的接触還元のための装置;
前記選択還元触媒のための装置の下流に組み込まれた、触媒層によって好ましくは少なくとも部分的に覆われた、ディーゼル粒子フィルター;
前記選択的接触還元のための装置の上流及び/又は、選択的接触還元のための装置とディーゼル粒子フィルターとの間に組み込まれた接触酸化のための装置;
前記選択的接触還元のための装置の入口に注入される制御された量の還元剤を注入するための装置;及び
前記接触酸化のための装置の入口に注入される制御された量の炭化水素を注入するための装置;
を含む系におけるディーゼルエンジンからの排ガスを浄化する方法であって、前記ディーゼル粒子フィルターが、還元剤の注入を閉じることによって受動的に再生され、そして前記ディーゼル粒子フィルターが、接触酸化のための装置の少なくとも一つの入口への炭化水素の注入を開放し、そして任意に還元剤の注入を閉じることによって能動的に再生されることを特徴とする、上記方法。 - 前記フィルターが500℃までの温度においてNO2により受動的に再生される、請求項1に記載の方法。
- 前記フィルターが500℃〜700℃の温度で能動的に再生される、請求項1に記載の方法。
- 前記還元剤が、アンモニア、アンモニア水溶液、尿素、尿素水溶液、シアヌル酸、アンメリド(ammelide)、アンメリンゲ(ammelinge)、シアヌル酸アンモニウム、ビウレット、カルバミン酸アンモニウム、炭酸アンモニウム、ギ酸アンモニウム、メラミン、又はトリシアノウレアである、請求項1に記載の方法。
- 前記還元剤が、アンモニア、アンモニア水溶液、尿素、尿素水溶液又はシアヌル酸である、請求項4に記載の方法。
- 前記炭化水素が、燃料、好ましくはディーゼルエンジンに対するのと同じ燃料である、請求項1に記載の方法。
- 前記選択的接触還元が、バナジウムベース触媒、又はゼオライトベース触媒、又は機能化酸性卑金属混合酸化物触媒の存在下で起こる、請求項1に記載の方法。
- 前記バナジウムベース触媒が、タングステン酸化物又はモリブデン酸化物が追加され得る、チタン酸化物上のバナジウム酸化物であり、前記ゼオライトベース触媒が、銅及び/又は鉄変性βゼオライト、ZSM−5又はチャバザイト(chabasite)であり、そして前記機能化酸性卑金属混合酸化物触媒が、酸性のセリウム−ジルコニウム酸化物混合物及びジルコニウム−チタン酸化物混合物からなる、請求項7に記載の方法。
- 前記バナジウムベース触媒が、150℃〜550℃の温度で使用され、そして前記ゼオライトベース触媒が、150℃〜800℃の温度で使用される、請求項7に記載の方法。
- 前記ディーゼル粒子フィルター上の前記触媒層が、任意に貴金属、好ましくはパラジウム及び白金と組み合わされた卑金属酸化物類の混合物を含む、請求項1に記載の方法。
- 前記選択的接触還元装置の上流に第一の酸化触媒が組み込まれ、そして前記選択的接触還元装置と前記ディーゼル粒子フィルターとの間に第二の酸化触媒が組み込まれ、そしてアンモニアが該第一の酸化触媒入口に注入される、請求項1に記載の方法。
- 前記選択的接触還元のための装置の上流に組み込まれた前記接触酸化のための装置が、ランタン酸化物促進アルミニウム酸化物上の白金及びパラジウム、又はケイ素酸化物促進チタン酸化物上の白金及びパラジウム、又はジルコニウム酸化物促進セリウム酸化物上の白金及びパラジウムを含む触媒を含み、そして前記選択的接触還元のための装置の下流に組み込まれた前記接触酸化のための装置が、ランタン酸化物促進アルミニウム酸化物上のパラジウム、又はケイ素酸化物促進チタン酸化物上のパラジウム、又はジルコニウム酸化物促進セリウム酸化物上のパラジウム、又は銅酸化物及びマンガン酸化物の混合物、又は銅酸化物及びマンガン酸化物の混合物上のパラジウムを含む触媒を含む、請求項1に記載の方法。
- 前記フィルターにわたる圧力降下が測定され、そして還元剤の追加及び炭化水素の追加を制御するために、生成した信号が使用される、請求項1に記載の方法。
- 請求項1〜13のいずれか一つに記載の方法を使用するためのシステム。
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