JP2019162622A - ゾーン化ディーゼル酸化触媒 - Google Patents
ゾーン化ディーゼル酸化触媒 Download PDFInfo
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- JP2019162622A JP2019162622A JP2019056137A JP2019056137A JP2019162622A JP 2019162622 A JP2019162622 A JP 2019162622A JP 2019056137 A JP2019056137 A JP 2019056137A JP 2019056137 A JP2019056137 A JP 2019056137A JP 2019162622 A JP2019162622 A JP 2019162622A
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- washcoat
- oxidation catalyst
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/103—Oxidation catalysts for HC and CO only
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
基材;
基材上に配置又は担持される第一のウォッシュコート領域、該第一のウォッシュコート領域は、第一の白金族金属(PGM)及び第一の担体材料を含む;
第一のウォッシュコート領域に隣接する第二のウォッシュコート領域、該第二のウォッシュコート領域は、第二の白金族金属(PGM)及び第二の担体材料を含む;
基材上に配置又は担持される第三のウォッシュコート領域、該第三のウォッシュコート領域は、第三の白金族金属(PGM)及び第三の担体材料を含む;
を含み:かつ、
(i)第三のウォッシュコート領域が第二のウォッシュコート領域に隣接する;又は
(ii)第二のウォッシュコート領域が第三のウォッシュコート領域上に配置又は担持されるかのいずれかである。
(i)長さL1の第一のウォッシュコートで基材をコートすること、基材は軸長Lを有し、L1は軸長Lより短いか又は等しい(例えば、L1≦L);その後、
(ii)長さL2の第二のウォッシュコートで基材をコートすること、該L2は軸長Lより短いか又は等しい(例えば、L2≦L);
(iii)基材上の第一のウォッシュコート及び第二のウォッシュコートを乾燥させること;
(iv)第一のウォッシュコート及び第二のウォッシュコートの少なくとも一つを白金族金属で長さL3含浸すること、該L3は軸長Lよりも短い(L3<L);並びに
(v)第一のウォッシュコート、第二のウォッシュコート及び含浸された白金族金属、でコートされた基材を焼成すること、を含む。
(i)長さL1の第一のウォッシュコートで第一の端から基材をコートすること、基材は軸長Lを有し、L1は軸長Lより短い(例えば、L1<L);その後、
(ii)長さL2の第二のウォッシュコートで第二の端から基材をコートすること、該L2は、LとL1の差より大きい(例えば、L2>LーL1);及び
(iii)第一のウォッシュコート及び第二のウォッシュコートでコートされた基材を焼成すること、を含む。
ここで用いられる「PGM」という頭字語は、「白金族金属(platinum group metal)」を指す。「白金族金属(platinum group metal)」という用語は、周期表の金属Ru、Rh、Pd、Os、Ir及びPt、特に金属Ru、Rh、Pd、Ir及びPtを一般に指す。
ゾーン化ディーゼル酸化触媒(ゾーン化DOC)は、本発明の第二の方法態様に従って、及び、国際公開番号99/47260号に記載のように調製された。ゾーン化(DOC)は、図4に示される構造を有する。第一のウォッシュコート領域(1)の長さ(例えば、L−L2)は、基材の長さ(例えば、L)の25%であった。第一のウォッシュコート領域において、白金のローディングは26.7g ft−3、パラジウムのローディングは26.7g ft−3であった。第二のウォッシュコート領域(2)の長さ(例えば、L2+L1−L)は、基材の長さの20%であった。第二のウォッシュコート領域において、白金のローディングは34.7g ft−3、パラジウムのローディングは26.7g ft−3であった。第三のウォッシュコート領域(3)の長さ(例えば、L−L1)は、基材の長さの55%であった。第三のウォッシュコート領域における白金のローディングは8g ft−3であり、パラジウムは存在しなかった。触媒のPGM(例えば、白金及びパラジウム)の総ローディングは、30g ft−3であった。酸化触媒における、白金の総質量のパラジウムの総質量に対する比は1.5:1であった。
ゾーン化DOC及び参照DOCのNO酸化活性が測定され、結果は図5に示される。ゾーン化DOCが40g ft−3の全PGMローディングを有する参照DOCよりも低い30g ft−3の全PGMローディングを有するにも関わらずゾーン化DOC(▲)は、参照DOC(◆)よりも優れたNO酸化活性を示す。
ゾーン化DOC及び参照DOCは、DOC+CSFフィルタ構成において、610℃における50及び100時間の7L IT4エンジンでの老化の前後で試験された。ゾーンDOC及び参照DOCは、クエンチ試験において比較された。ディーゼル燃料が各触媒に注入され、発熱を生じ、触媒を離れる排ガス温度は610℃であった。発熱生成は、定常状態の温度及び流動状態(エンジンの速度及び負荷)で安定化され、その後、触媒入口の温度が低下されるようにエンジンの負荷が低下された。触媒入口の温度が低すぎて発熱生成を続けられなくなったとき、触媒はクエンチする。結果は図6及び7に示される。図6に見られ得るように、参照DOCは270℃でクエンチする。対照的に、ゾーン化DOCは、同じ条件下でクエンチせず(図7を参照)、参照DOCに比べ、それが優れたHC酸化活性を有することを示す。ゾーン化DOCは、参照DOCより低温で、そのHC酸化性能を維持する。これは、ゾーン化DOCが低運転温度においてフィルタ基材を含む排出制御装置を再生するために用いられ得ることを示す。各触媒からのHCスリップも同じ触媒入口温度及び流動条件下で試験された。図8に示される結果は、約880kg h−1の排気流、75k h−1のGHSVで得られ、触媒入口及び出口温度は、それぞれ340及び610℃であった。図9に示される結果は、約1050kg h−1の排気流、115k h−1GHSVで得られ、触媒入口及び出口温度は、それぞれ330及び610℃であった。ゾーン化触媒は、参照DOCよりも低いHCスリップを示す。
ゾーン化DOC及び参照DOCは、低Sディーゼル(1.5g L−1の硫黄)でそれぞれ硫化され、NO酸化性能が275℃で測定された。ゾーン化DOCは、S曝露の後、参照DOCよりも小さくNO酸化性能を失うことが図10から見られ得る。参照DOCは、同じ温度における再生の後に部分的に回復する一方で、ゾーン化DOCは、再生の後に完全に回復もする。各触媒についての再生の間のHCスリップは、硫酸化の後に変化しなかった。
Claims (31)
- ディーゼルエンジンからの排ガスを処理するための酸化触媒であって、
基材;
基材上に配置される第一のウォッシュコート領域であって、第一の白金族金属(PGM)及び第一の担体材料を含む第一のウォッシュコート領域;
第一のウォッシュコート領域に隣接する第二のウォッシュコート領域であって、第二の白金族金属(PGM)及び第二の担体材料を含む第二のウォッシュコート領域;
基材上に配置される第三のウォッシュコート領域であって、第三の白金族金属(PGM)及び第三の担体材料を含む第三のウォッシュコート領域;
を含み:かつ、
(i)第三のウォッシュコート領域が第二のウォッシュコート領域に隣接するか;又は
(ii)第二のウォッシュコート領域が第三のウォッシュコート領域上に配置されるかのいずれかである、酸化触媒。 - 第三のウォッシュコート領域が第二のウォッシュコート領域に隣接する、請求項1に記載の酸化触媒。
- 第一のウォッシュコート領域が第一のウォッシュコートゾーンを含み、第二のウォッシュコート領域が第二のウォッシュコートゾーンを含み、第三のウォッシュコート領域が第三のウォッシュコートゾーンを含む、請求項2に記載の酸化触媒。
- 第三のPGMが白金である、請求項3に記載の酸化触媒。
- 第二のPGMが白金及びパラジウムの組合せである、請求項3又は4に記載の酸化触媒。
- 第一のウォッシュコート領域が上流のウォッシュコート層の一部を含み、第二のウォッシュコート領域が上流のウォッシュコート層の一部及び下流のウォッシュコート層の一部を含み、第三のウォッシュコート領域が下流のウォッシュコート層の一部を含む、請求項2に記載の酸化触媒。
- 第二のウォッシュコート領域が、下流のウォッシュコート層の前部上に配置される上流のウォッシュコート層の後部を含む、請求項6に記載の酸化触媒。
- 第一のPGMが白金であり、第三のPGMが白金及びパラジウムの組合せであり、第二のPGMが白金及びパラジウムの組合せである、請求項7に記載の酸化触媒。
- 第二のウォッシュコート領域が、上流のウォッシュコート層の後部上に配置される下流のウォッシュコート層の前部を含む、請求項6に記載の酸化触媒。
- 第一のPGMが白金及びパラジウムの組合せであり、第三のPGMが白金であり、第二のPGMが白金及びパラジウムの組合せである、請求項9に記載の酸化触媒。
- 第二のウォッシュコート領域が第三のウォッシュコート領域上に配置される、請求項1に記載の酸化触媒。
- 第一のウォッシュコート領域が第一のウォッシュコート層又は第一のウォッシュコートゾーンを含み、第二のウォッシュコート領域が第二のウォッシュコート層を含み、第三のウォッシュコート領域が第三のウォッシュコート層を含む、請求項11に記載の酸化触媒。
- 第一のウォッシュコート領域が第一のウォッシュコート層からなる、請求項12に記載の酸化触媒。
- 第一のウォッシュコートゾーンが第一のウォッシュコート層及び第四のウォッシュコート層を含み、第四のウォッシュコート層が第一のウォッシュコート層上に配置される、請求項12に記載の酸化触媒。
- 第三のPGMの総ローディングが、第二のPGMの総ローディングより大きいか、又は等しい、請求項14に記載の酸化触媒。
- 第二のPGMの総ローディングが、第三のPGMの総ローディングより大きい、請求項1から14のいずれか一項に記載の酸化触媒。
- 第一のPGMの総ローディングが、第三のPGMの総ローディングより大きい、請求項1から16のいずれか一項に記載の酸化触媒。
- 第二のPGMの総ローディングが、第一のPGMの総ローディングより大きい、請求項1から17のいずれか一項に記載の酸化触媒。
- 第一のPGMが白金である、請求項1から18のいずれか一項に記載の酸化触媒。
- 第一のPGMがパラジウムである、請求項1から14のいずれか一項に記載の酸化触媒。
- 第一のPGMが、白金並びに白金及びパラジウムの組合せからなる群から選択される、請求項1から18のいずれか一項に記載の酸化触媒。
- 第二のPGMが、白金並びに白金及びパラジウムの組合せからなる群から選択される、請求項1から21のいずれか一項に記載の酸化触媒。
- 第三のPGMが、白金並びに白金及びパラジウムの組合せからなる群から選択される、請求項1から22のいずれか一項に記載の酸化触媒。
- 第一の担体材料が、アルミナ、シリカ、チタニア、ジルコニア、セリア及びそれらの二つ以上の混合又は複合酸化物からなる群から選択される耐火性金属酸化物を含む、請求項1から23のいずれか一項に記載の酸化触媒。
- 第二の担体材料が、アルミナ、シリカ、チタニア、ジルコニア、セリア及びそれらの二つ以上の混合又は複合酸化物からなる群から選択される耐火性金属酸化物を含む、請求項1から24のいずれか一項に記載の酸化触媒。
- 第三の担体材料が、アルミナ、シリカ、チタニア、ジルコニア、セリア及びそれらの二つ以上の混合又は複合酸化物からなる群から選択される耐火性金属酸化物を含む、請求項1から25のいずれか一項に記載の酸化触媒。
- 請求項1から26のいずれか一項に記載の酸化触媒と排出制御装置とを含む排気システム。
- ディーゼルエンジンと、(a)請求項1から26のいずれか一項に記載の酸化触媒又は(b)請求項27に記載の排気システムのいずれかとを含む車両。
- 請求項1から26に記載の酸化触媒の製造方法であって:
(i)長さL1の第一のウォッシュコートで基材をコートすることであって、基材が軸長Lを有し、L1≦Lであること;その後、
(ii)長さL2の第二のウォッシュコートで基材をコートすることであって、L2≦Lであること;
(iii)基材上の第一のウォッシュコート及び第二のウォッシュコートを乾燥させること;
(iv)第一のウォッシュコート及び第二のウォッシュコートの少なくとも一つを白金族金属で長さL3含浸することであって、L3<Lであること;及び、
(v)第一のウォッシュコート、第二のウォッシュコート及び含浸された白金族金属、でコートされた基材を焼成すること、
を含む、製造方法。 - 請求項1から26に記載の酸化触媒の製造方法であって:
(i)長さL1の第一のウォッシュコートで第一の端から基材をコートすることであって、基材が軸長Lを有し、L1<Lであること;その後、
(ii)長さL2の第二のウォッシュコートで第二の端から基材をコートすることであって、L2>LーL1であること;及び
(iii)第一のウォッシュコート及び第二のウォッシュコートでコートされた基材を焼成すること、
を含む、製造方法。 - フィルタ基材を有する排出制御装置の再生における、請求項1から26のいずれか一項に記載の酸化触媒の使用。
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GBGB1315892.8A GB201315892D0 (en) | 2013-07-31 | 2013-09-06 | Zoned diesel oxidation catalyst |
GBGB1316278.9A GB201316278D0 (en) | 2013-07-31 | 2013-09-12 | Zoned diesel oxidation catalyst |
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