JP7007296B2 - 3区画(theree-zone)ディーゼル酸化触媒 - Google Patents
3区画(theree-zone)ディーゼル酸化触媒 Download PDFInfo
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- JP7007296B2 JP7007296B2 JP2018554401A JP2018554401A JP7007296B2 JP 7007296 B2 JP7007296 B2 JP 7007296B2 JP 2018554401 A JP2018554401 A JP 2018554401A JP 2018554401 A JP2018554401 A JP 2018554401A JP 7007296 B2 JP7007296 B2 JP 7007296B2
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- oxidation catalyst
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- diesel oxidation
- diesel
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- 238000007254 oxidation reaction Methods 0.000 title claims description 45
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 65
- 239000000126 substance Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 33
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 24
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 241000953555 Theama Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
排ガスが連続的に接触するよう、排ガスの流れる方向に、組成の異なる材料区画を有する、予め区画化された酸化触媒も記載されている。
担持体上に配置された触媒活性物質区画A、B、及びCと、を含む、ディーゼル酸化触媒に関し、
物質区画Aが、パラジウム又はPt:Pd重量比1以下の白金及びパラジウムと、アルカリ土類金属とを含有し、かつ端面aから長さLの20~80%まで延び、
物質区画Bが、酸化セリウムを含有し、白金を含まず、かつ端面bから長さLの20~80%まで延び、
物質区画Cが、白金又はPt:Pd重量比5以上の白金及びパラジウムを含有し、かつ
物質区画Aと物質区画Cのいずれも、物質区画Bの上方には配置されていない。
a)寸法14.38cm×10.16cm(5.66”×4.00”)、セル密度が1平方センチメートルあたり62セル(400cpsi)、壁厚0.16mm(6.5ミル)の市販のコージライト製の丸形フロースルー基材を、その全長に、49.23g/Lのランタンドープされたメソ多孔性酸化アルミニウム、0.60540g/Lの標準水溶性Pt化合物、及び0.10090g/Lの標準水溶性Pd化合物を含有するウォッシュコートでコーティングした。Pt:Pd重量比は6:1とした。
ステップc)を省略するという違いを加えて実施例1を繰り返した。
ステップb)を省略するという違いを加えて実施例1を繰り返した。
a)寸法14.38cm×10.16cm(5.66”×4.00”)、セル密度が1平方センチメートルあたり62セル(400cpsi)、壁厚0.16mm(6.5ミル)の市販のコージライト製のフロースルー基材を、その全長に、73.85g/Lのランタンドープされたメソ多孔性酸化アルミニウム、0.90810g/Lの標準水溶性Pt化合物、及び0.15135g/Lの標準水溶性Pd化合物を含有するウォッシュコートでコーティングした。Pt:Pd重量比は6:1とした。
a)寸法14.38cm×10.16cm(5.66”×4.00”)、セル密度が1平方センチメートルあたり62セル(400cpsi)、壁厚0.16mm(6.5ミル)の市販のコージライト製のフロースルー基材を、一端(以下に記載の試験における流入面上)からその長さの50%超までを、48.23g/Lの市販のランタンドープされた酸化アルミニウム、1.00g/Lの酸化ストロンチウム(例えば、Sr(OH)2)、0.47086g/Lの標準水溶性Pd化合物、及び0.23543g/Lの標準水溶性Pt化合物を含有するウォッシュコートでコーティングした。Pt:Pd重量比は1:2とした。
寸法14.38cm×10.16cm(5.66”×4.00”)、セル密度が1平方センチメートルあたり62セル(400cpsi)、壁厚0.16mm(6.5ミル)の市販のコージライト製のフロースルー基材を、長さの等しい3つの部材に切り分けた。
この3つの部材を、それらの全長に実施例1a)、b)、及びc)において言及するウォッシュコート材料でそれぞれコーティングした。
以下に説明する試験のため、3つの基材の部材を、排ガスが流れる方向に次の順で共に接合した:
第1の部材は、実施例1b)によるウォッシュコートでコーティングした。
第2の部材は、実施例1a)によるウォッシュコートでコーティングした。
第3の部材は、実施例1c)によるウォッシュコートでコーティングした。
a)水熱炉によるエージング(aging)
実施例1~3及び比較例1~3の触媒を、750℃で16時間エージングさせた(aged)。別途記載のない限り、この方法でエージングさせた触媒を使用して、以下に記載の比較試験を実施した。
空間速度=37,500 1/時間
ボア(Bore)のコア寸法は2.54cm×10.16cm(1”×4”)(実施例1~3、及び比較例1~3の基材にボアを形成(bored from))
試験した温度範囲:75℃~500℃。200、250、及び300℃の温度での値を以下の表に記載する。
傾斜/加熱速度=15K/分
エンジンの回転速度を一定にしてトルクを上昇させることにより、プレ触媒の温度を上昇させる;この試験は、モデルガス法と同様に、低温から高温で実施する。
汚染物質の変換は、AMAラインで測定し、算出する;CLD法により、NO2の形成を測定する。
定置エンジン動作点は、トルクと回転速度とを適切に組み合わせることにより近づける。これを一定時間一定に保つ;次に、第2の/外部注入器により、触媒の上流に微細に噴霧化させた状態でディーゼル燃料を注入した後、燃料を変換し、ある種の発熱/熱を生成し、これを触媒に取り付けた熱電対により測定する。
試験は、高温から低温で実施する;温度は:
1)280℃プレ触媒の温度
2)270℃プレ触媒の温度
3)260℃プレ触媒の温度とする。
e)白金の移動(platinum migration)の測定
等温反応器を備えた標準的な合成ガスプラントにおいて、実施例1~3及び比較例1~3に使用した触媒を、新しい状態で以下の組成のモデルガスに一定温度の650℃で18時間暴露した:
Claims (14)
- 第1の端面a及び第2の端面bの間に延びる長さLを有する担持体と、
前記担持体上に配置された触媒活性物質区画A、B、及びCと、を含む、ディーゼル酸化触媒であって、
物質区画Aが、白金なしのパラジウム又はPt:Pd重量比1以下の白金及びパラジウムと、アルカリ土類金属とを含有し、かつ流入側の端面aから長さLの20~80%まで延び、
物質区画Bが、酸化セリウムを含有し、白金を含まず、かつ流出側の端面bから長さLの20~80%まで延び、
物質区画Cが、パラジウムなしの白金又はPt:Pd重量比5以上の白金及びパラジウムを含有し、かつ
物質区画Aと物質区画Cのいずれも、物質区画Bの上方には配置されていない、ディーゼル酸化触媒。 - 前記物質区画A及びCにおいて、担持酸化物上に、パラジウム、白金、又は白金及びパラジウムが存在することを特徴とする、請求項1に記載のディーゼル酸化触媒。
- 前記物質区画A及びCにおける担持酸化物が、互いに同一であり又は異なっており、酸化アルミニウム、ドープされた酸化アルミニウム、酸化ケイ素、二酸化チタン、及びこれらの1つ以上の混合した酸化物からなる群から選択されることを特徴とする、請求項1及び/又は2に記載のディーゼル酸化触媒。
- 前記物質区画Aにおけるアルカリ土類金属が、前記物質区画Aの重量に対し0.5~5重量%の量で存在することを特徴とする、請求項1~3のいずれか一項に記載のディーゼル酸化触媒。
- 前記物質区画Aにおけるアルカリ土類金属が、ストロンチウム若しくはバリウム、又はストロンチウム及びバリウムであることを特徴とする、請求項1~4のいずれか一項に記載のディーゼル酸化触媒。
- 物質区画Bが、パラジウムを含有することを特徴とする、請求項1~5のいずれか一項に記載のディーゼル酸化触媒。
- 物質区画Bが、前記物質区画Bの重量に対し0.01~5重量%の量でパラジウムを含有することを特徴とする、請求項6に記載のディーゼル酸化触媒。
- 物質区画Cが、前記担持体の全長Lにわたって延在することを特徴とする、請求項1~7のいずれか一項に記載のディーゼル酸化触媒。
- 物質区画A及びBが物質区画C上に配置されることを特徴とする、請求項1~8のいずれか一項に記載のディーゼル酸化触媒。
- 物質区画Cが物質区画A上に配置され、物質区画Bが物質区画C上に配置されることを特徴とする、請求項1~8のいずれか一項に記載のディーゼル酸化触媒。
- 物質区画A及びBのそれぞれが、前記担持体の前記長さLの50%まで延在し、かつ物質区画Cが前記担持体の長さLの100%まで延在することを特徴とする、請求項1~10のいずれか一項に記載のディーゼル酸化触媒。
- ディーゼル排ガスを処理するための方法であって、前記ディーゼル排ガスを、請求項1~11のいずれか一項に記載のディーゼル酸化触媒に通すことを特徴とし、前記ディーゼル排ガスは、前記端面aで前記担持体に流入し、前記端面bで前記担持体から流出する、方法。
- 請求項1~11のいずれか一項に記載のディーゼル酸化触媒を有する、ディーゼルエンジンからの排ガスを浄化する装置。
- 請求項1~11のいずれか一項に記載のディーゼル酸化触媒が、ディーゼル微粒子フィルター及び/又は窒素酸化物の選択的触媒還元のための触媒の上流に配置されていることを特徴とする、請求項13に記載の装置。
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2016
- 2016-05-02 DE DE102016207484.9A patent/DE102016207484A1/de active Pending
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2017
- 2017-05-02 WO PCT/EP2017/060350 patent/WO2017191099A1/de unknown
- 2017-05-02 JP JP2018554401A patent/JP7007296B2/ja active Active
- 2017-05-02 US US16/092,806 patent/US10767528B2/en active Active
- 2017-05-02 CN CN201780026882.0A patent/CN109475843B/zh active Active
- 2017-05-02 EP EP17723648.6A patent/EP3452214B1/de active Active
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WO2015015182A1 (en) | 2013-07-31 | 2015-02-05 | Johnson Matthey Public Limited Company | Zoned diesel oxidation catalyst |
WO2015095058A1 (en) | 2013-12-16 | 2015-06-25 | Basf Corporation | Manganese-containing diesel oxidation catalyst |
WO2015110818A1 (en) | 2014-01-23 | 2015-07-30 | Johnson Matthey Public Limited Company | Diesel oxidation catalyst and exhaust system |
Also Published As
Publication number | Publication date |
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CN109475843B (zh) | 2022-05-27 |
US20190162095A1 (en) | 2019-05-30 |
JP2019521835A (ja) | 2019-08-08 |
CN109475843A (zh) | 2019-03-15 |
EP3452214A1 (de) | 2019-03-13 |
US10767528B2 (en) | 2020-09-08 |
EP3452214B1 (de) | 2022-11-23 |
DE102016207484A1 (de) | 2017-11-02 |
WO2017191099A1 (de) | 2017-11-09 |
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