JP2017508606A - ディーゼル酸化触媒及び排気系統 - Google Patents
ディーゼル酸化触媒及び排気系統 Download PDFInfo
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- JP2017508606A JP2017508606A JP2016548194A JP2016548194A JP2017508606A JP 2017508606 A JP2017508606 A JP 2017508606A JP 2016548194 A JP2016548194 A JP 2016548194A JP 2016548194 A JP2016548194 A JP 2016548194A JP 2017508606 A JP2017508606 A JP 2017508606A
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
Description
(a)第1のウオッシュコート領域の上に配置又は支持される(例えば図2、4及び5参照);及び/又は
(b)基材の上に直接配置される[即ち第2のウオッシュコート領域は基材の表面と接する](例えば図1、3、4参照);及び/又は
(c)第1のウオッシュコート領域と接する[即ち第2のウオッシュコート領域は第1のウオッシュコート領域と隣接又は境界を接する]。
(i)第2のウオッシュコート領域の上に配置又は支持される(例えば図3及び4参照);及び/又は
(ii)基材の上に直接配置される[即ち第1のウオッシュコート領域は基材の表面と接する](例えば図3及び4参照);及び/又は
(iii)第2のウオッシュコート領域と接する[即ち第1のウオッシュコート領域は第2のウオッシュコート領域と隣接又は境界を接する]。
(a)第3のウオッシュコート領域の上に配置又は支持されうる(例えば図6、8及び10参照);及び/又は
(b)基材の上に直接配置されうる[即ち第2のウオッシュコート領域は基材の表面と接する];及び/又は
(c)第3のウオッシュコート領域と接しうる[即ち第2のウオッシュコート領域は第3のウオッシュコート領域と隣接又は接触する]。
(a)第2のウオッシュコート領域が基材の出口端に配置された第2のウオッシュコートゾーンであり、任意選択的に第1のウオッシュコート領域が基材の入口端に配置された第1のウオッシュコートゾーンであるとき;
(b)第1のウオッシュコート領域が第1のウオッシュコート層であり、第2のウオッシュコート領域が第2のウオッシュコートゾーンであり、第2のウオッシュコートゾーンが基材の出口端において第1のウオッシュコート層の上に配置されるとき;又は
(c)第1のウオッシュコート領域が第1のウオッシュコート層であり、第2のウオッシュコート領域が第2のウオッシュコート層であり、第2のウオッシュコート層が第1のウオッシュコート層の上に配置されるとき、
第1のウオッシュコート領域と接触した後の排気ガスと接触するように配置又は配向される。
また、予想外に、第2のゼオライト触媒の実施態様のゼオライト触媒を含むウオッシュコート領域が、コールドスタート触媒(CSCTM)活性を有することが判明した。このような活性は、比較的低い排気ガス温度(例えば200℃未満)においてNOx及び炭化水素(HC)を吸着することにより、コールドスタート期間の間の排出を低減することができる。吸着したNOx及び/又はHCは、ゼオライト触媒の温度がNO及び/又はHCを酸化するための他の触媒成分の実効温度に近い又は同実効温度を上回るとき、ウオッシュコート領域により放出される。ゼオライト触媒のコールドスタート触媒活性は、マンガンを含有する第2のウオッシュコート領域と組み合わせたとき、特に有益である。
「ウオッシュコート」という用語は、当技術分野において周知であり、通常酸化触媒の製造の間に、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鎖端(例えば遮蔽又は閉塞された端部)よりも入口チャネルの入口端(例えば開放端)に近いウオッシュコートゾーン、及び/又は
(b)基材の出口チャネルの出口端(例えば開放端)よりも出口チャネルの閉鎖端(例えば遮蔽又は閉塞された端部)に近いウオッシュコートゾーン
を指す。
(a)基材の出口チャネルの閉鎖端(例えば遮蔽又は閉塞された)よりも出口チャネルの出口端(例えば開放端)に近いウオッシュコートゾーン、及び/又は
(b)基材の入口チャネルの入口端(例えば開放端)よりも入口チャネルの閉鎖端(例えば遮蔽又は閉塞された端部)に近いウオッシュコートゾーン
を指す。
シリカ−アルミナ粉末を、水中においてスラリー化し、d90<20ミクロンまで粉砕した。可溶性の白金塩を加え、混合物を撹拌して均質にした。スラリーを、確立されたコーティング技術を用いて、一平方インチ当たり400個の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。次いでそれを乾燥し、500℃でか焼した。この部分のPtローディングは30g ft−3であった。
実施例1の方法を繰り返し、但し混合物を撹拌して均質にする前に、可溶性白金塩と、続いて硝酸マンガンを加えた。この部分へのPtローディングは30g ft−3であった。この部分へのマンガンのローディングは40g ft−3であった。Pt対マンガンの重量比は3:4であった。
実施例2の方法を使用し、但しシリカ−アルミナ粉末の代わりに、アルミナ粉末を水中においてスラリー化し、d90<20ミクロンまで粉砕した。この部分へのPtローディングは30g ft−3であった。この部分へのマンガンのローディングは40g ft−3であった。Pt対マンガンの重量比は3:4であった。
シリカでドープされたアルミナ粉末を、水中においてスラリー化し、d90<20ミクロンまで粉砕した。酢酸バリウムをスラリーに加え、続いて適量の可溶性白金及びパラジウム塩を加えた。スラリーが、シリカでドープされたアルミナとゼオライトとを、質量でそれぞれ78%と22%含むように、ベータゼオライトを加えた。次いでスラリーを撹拌して均質にした。得られたウオッシュコートを、確立されたコーティング技術を用いて、一平方インチ当たり400個のセルを有するコーディエライトフロースルーモノリスの入口チャネルに塗布し、次いで乾燥した。
シリカでドープされたアルミナ粉末を、水中においてスラリー化し、d90<20ミクロンまで粉砕した。酢酸バリウムをスラリーに加え、続いて適量の可溶性白金及びパラジウム塩を加えた。スラリーが、シリカでドープされたアルミナとゼオライトとを、質量でそれぞれ78%と22%含むように、ベータゼオライトを加えた。次いでスラリーを撹拌して均質にした。得られたウオッシュコートを、確立されたコーティング技術を用いて、一平方インチ当たり400個のセルを有するコーディエライトフロースルーモノリスの入口チャネルに塗布し、次いで乾燥した。
NO酸化の測定
実施例1から5の触媒の各々からコアの試料を採取した。すべてのコアは、750℃のオーブンで15時間にわたり熱水的に「老化」させた。実施例4及び5から更にコアを取り、「新品の」状態に保った(即ちオーブンによる熱処理を行わずに)。
SCATの結果を以下の表2から4に示す。
Pdナイトレートを、CHA構造を有する小孔径のゼオライトのスラリーに加え、撹拌した。スラリーを、確立されたコーティング技術を用いて、一平方インチ当たり400個のセルの構造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し、500℃でか焼した。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40g ft−3であった。
Pdナイトレートを、CHA構造を有する小孔径のゼオライトのスラリーに加え、撹拌した。スラリーを、確立されたコーティング技術を用いて、一平方インチ当たり400個のセルの構造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し、500℃でか焼した。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40g ft−3であった。
NO酸化の測定
実施例6及び7の触媒からコアの試料を採取した。両方のコアは、800℃のオーブンで16時間にわたり、10%の水中で、熱水的に老化させた。
SCATの結果を以下の表6に示す。
Claims (30)
- ディーゼルエンジンの排気ガスを処理するための酸化触媒であって:
第1の白金族金属(PGM)及び第1の支持材を含む、一酸化炭素(CO)及び炭化水素(HC)を酸化するための第1のウオッシュコート領域;
白金(Pt)、マンガン(Mn)及び第2の支持材を含む、一酸化窒素(NO)を酸化するための第2のウオッシュコート領域、並びに
入口端及び出口端を有する基材;
を備え、第2のウオッシュコート領域が、基材の出口端において、排気ガスが第1のウオッシュコート領域と接触した後で、排気ガスと接触するように配置されている、酸化触媒。 - 第2のウオッシュコート領域が、基材の出口端に配置された第2のウオッシュコートゾーンである、請求項1に記載の酸化触媒。
- 第1のウオッシュコート領域が、基材の入口端に配置された第1のウオッシュコートゾーンである、請求項1又は2に記載の酸化触媒。
- 第1のウオッシュコート領域が第1のウオッシュコートゾーンであり、第2のウオッシュコート領域が第2のウオッシュコートゾーンであり、第1のウオッシュコートゾーンと第2のウオッシュコートゾーンは単層として基材上に配置される、請求項1から3のいずれか一項に記載の酸化触媒。
- 第1のウオッシュコート領域が第1のウオッシュコート層であり、第2のウオッシュコートゾーンが第1のウオッシュコート層である、請求項2に記載の酸化触媒。
- 第1のウオッシュコート領域が第1のウオッシュコート層であり、第2のウオッシュコート領域が第2のウオッシュコート層であり、第2のウオッシュコート層が第1のウオッシュコート層の上に配置される、請求項1に記載の酸化触媒。
- 第2のウオッシュコート層が基材の全長にわたって延びている、請求項6に記載の酸化触媒。
- 第2のウオッシュコート領域が、唯一の白金族金属として白金(Pt)を含む、請求項1から7のいずれか一項に記載の酸化触媒。
- 第2の支持材が、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うちの二つ以上の混合若しく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む、請求項1から8のいずれか一項に記載の酸化触媒。
- 第2の支持材が、ドーパントでドープされたアルミナを含む、請求項9に記載の酸化触媒。
- 第2の支持材が、シリカでドープされたアルミナを含む、請求項10に記載の酸化触媒。
- 第2のウオッシュコート領域が実質的にゼオライトを含まない、請求項1から11のいずれか一項に記載の酸化触媒。
- 第1の白金族金属(PGM)が、白金(Pt)、パラジウム(Pd)及びこれらの組合せからなる群より選択される、請求項1から12のいずれか一項に記載の酸化触媒。
- 第1の支持材が、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うちの二つ以上の混合若しく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む、請求項1から13のいずれか一項に記載の酸化触媒。
- 第1の支持材が、ドーパントでドープされたアルミナを含む、請求項14に記載の酸化触媒。
- 第1の支持材が、シリカでドープされたアルミナを含む、請求項15に記載の酸化触媒。
- 第1のウオッシュコート領域が炭化水素吸着材を更に含む、請求項1から16のいずれか一項に記載の酸化触媒。
- 第1のウオッシュコート領域がアルカリ土類金属を更に含む、請求項1から17のいずれか一項に記載の酸化触媒。
- 第3のウオッシュコート領域を更に含む、請求項1から18のいずれか一項に記載の酸化触媒。
- 第3のウオッシュコート領域が、基材の上に直接配置されている、請求項19に記載の酸化触媒。
- 第3のウオッシュコート領域が、第1のウオッシュコート領域及び/又は第2のウオッシュコート領域の上に配置されている、請求項19又は20に記載の酸化触媒。
- 第3のウオッシュコート領域がゼオライト触媒を含み、ゼオライト触媒は、貴金属、ゼオライト、及び任意選択的に卑金属を含む、請求項19から21のいずれか一項に記載の酸化触媒。
- 貴金属がパラジウムである、請求項22に記載の酸化触媒。
- ゼオライトが、AEI、CHA又はAEI−CHA連晶であるフレームワークタイプを有する小孔径ゼオライトである、請求項22又は23に記載の酸化触媒。
- 基材がフロースルー基材である、請求項1から24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及び排出制御装置を備える排気系統。
- 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)、ディーゼルパティキュレートフィルター(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、及びこれらのうちの二つ以上の組み合わせからなる群より選択される、請求項26に記載の排気系統。
- ディーゼルエンジンと、請求項1から25のいずれか一項に記載の酸化触媒又は請求項26又は27に記載の排気系統とを備える、車両又は装置。
- ディーゼルエンジンの排気ガスの処理方法であって、排気ガスを請求項1から25のいずれか一項に記載の酸化触媒と接触させること、又は排気ガスを、請求項26又は27に記載の排気系統に通過させることを含む方法。
- ディーゼルエンジンの排気ガス中の一酸化窒素(NO)の酸化を増強するための、ディーゼルエンジン用酸化触媒におけるマンガン(Mn)の使用であって、酸化触媒が請求項1から25のいずれか一項に記載の酸化触媒である、使用。
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GBGB1401115.9A GB201401115D0 (en) | 2014-01-23 | 2014-01-23 | Diesel oxidation catalyst and exhaust system |
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GBGB1405871.3A GB201405871D0 (en) | 2014-01-23 | 2014-04-01 | Diesel oxidation catalyst and exhaust system |
GB1405871.3 | 2014-04-01 | ||
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