JPWO2019012874A1 - 排ガス浄化用触媒 - Google Patents
排ガス浄化用触媒 Download PDFInfo
- Publication number
- JPWO2019012874A1 JPWO2019012874A1 JP2018553161A JP2018553161A JPWO2019012874A1 JP WO2019012874 A1 JPWO2019012874 A1 JP WO2019012874A1 JP 2018553161 A JP2018553161 A JP 2018553161A JP 2018553161 A JP2018553161 A JP 2018553161A JP WO2019012874 A1 JPWO2019012874 A1 JP WO2019012874A1
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- partition
- catalyst
- gas purification
- cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000746 purification Methods 0.000 title claims description 117
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- -1 alumina (Al 2 O 3 ) Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 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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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 description 1
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- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/60—Discontinuous, uneven properties of filter material, e.g. different material thickness along the longitudinal direction; Higher filter capacity upstream than downstream in same housing
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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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
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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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
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Abstract
Description
なお、本出願は2017年7月11日に出願された日本国特許出願2017−135688号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
比較例1として、図4に示すような構成の排ガス浄化用触媒30を作製した。すなわち、A1部,B1部,C1部共に隔壁内部のみに触媒層を備えた排ガス浄化用触媒30を作製した。具体的には、先ず、図2に示すようなウォールフロー型の基材11(コージェライト製、体積:1.3L)を用意した。次に、硝酸ロジウム(Rh(NO3)3)と、アルミナ粉末(γ−Al2O3)と、ZC複合酸化物(ZrO2−CeO2)粉末と、硫酸バリウム(BaSO4)と、Al2O3系バインダとをイオン交換水中で混合して、Rhスラリーを調製した。また、硝酸パラジウム(Pd(NO3)2)と、アルミナ粉末と、ZC複合酸化物粉末と、硫酸バリウム(BaSO4)と、Al2O3系バインダとをイオン交換水中で混合して、Pdスラリーを調製した。
各例の排ガス浄化用触媒について、16万km相当の加速耐久試験を行った。具体的には、各例の排ガス浄化用触媒を排気量4.6Lのエンジンベンチの排気経路に設置し、エンジンを稼働させ、触媒床温度1000℃で46時間保持した。
上記耐久試験終了後の排ガス浄化用触媒について、排ガスの浄化性能を評価した。具体的には、先ず、各例の排ガス浄化用触媒をエンジンベンチの排気経路に設置し、熱交換器を用いて触媒入ガス温度を200℃から昇温速度10℃/minで昇温させた。このときの入ガス濃度と出ガス濃度との比からHC,CO,NOxの各成分の浄化率を連続的に測定して、各成分の浄化率が50%に達したときの触媒入ガス温度(50%浄化達成温度)をそれぞれ評価した。結果を図5に示す。なお、図5は、比較例1におけるHCの50%浄化達成温度を「基準(1.00)」としたときの相対値で表している。数値は、小数点第2位以下を四捨五入している。この値が小さいほど浄化性能が良好なことを表している。
比較例2として、図6に示すような構成の排ガス浄化用触媒40を作製した。すなわち、A2部において、隔壁16の表面に触媒層40aを備え、B2部において、隔壁16の片側の表面と内部とに触媒層40bを備え、C2部において、隔壁16の内部に触媒層40cを備えた排ガス浄化用触媒40を作製した。具体的には、先ず、試験例(1)−1に準じて、RhスラリーとPdスラリーとを調製した。次に、比較例1と同様にして、上記調製したPdスラリーを排ガス流出側の端部15から出側セル14に流入させ、X方向に沿って隔壁16の全長の70%にあたる部分に供給して、隔壁16の内部にコートした後、乾燥および焼成した。なお、基材11の体積あたりのPdスラリーのコート量は80g/Lとした。次に、上記調製したRhスラリーを排ガス流入側の端部13から入側セル12に流入させ、X方向に沿って隔壁16の全長の70%にあたる部分に供給して、入側セル12に接する隔壁16の表面にコートした。なお、基材11の体積あたりのRhスラリーのコート量は135g/Lとした。X方向の中途部分では、隔壁16の全長の40%の長さにおいて、隔壁16の内部のPdスラリーと、隔壁16の表面のRhスラリーとが重なっている。この状態で、基材11を乾燥および焼成した。これにより、X方向のコート幅La2が隔壁16の全長の30%であるA2部40a(コート量135g/L)と、X方向のコート幅Lb2が隔壁16の全長の40%であるB2部40b(コート量215g/L)と、X方向のコート幅Lc2が隔壁16の全長の30%であるC2部40c(コート量80g/L)とで構成された触媒層を備える排ガス浄化用触媒40を作製した。
体積が1.7Lの基材11を使用し、Rhスラリーのコート量を100g/Lとし、Pdスラリーのコート量を95g/gとし、かつ、A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcを、表3に示すように変更したこと以外は例2と同様に、例A〜Dの排ガス浄化用触媒を作製した。また、各スラリーのコート量と、A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcとを例Cと同じように変更したこと以外は比較例1と同様にして、比較例3の排ガス浄化用触媒を作製した。比較例3と例A〜Dの触媒層の仕様を、表3にまとめる。
上記した試験例(1)−1と同様に耐久試験を実施し、耐久試験終了後の排ガス浄化用触媒について暖機性を評価した。具体的には、先ず、各例の排ガス浄化用触媒をエンジンベンチの排気経路に設置し、熱交換器を用いて触媒入ガス温度を50℃から500℃まで一気に上昇させた。そして、入ガス濃度と出ガス濃度との比からHCの50%浄化達成時間を測定した。結果を図8に示す。なお、図8は、例Aの結果を「基準(1.000)」としたときの相対値で表している。この値が小さいほど暖機性が良好なことを表している。
上記作製した排ガス浄化用触媒について、圧損上昇率を評価した。具体的には、先ず、触媒層をコートする前のハニカム基材(リファレンス)を準備し、7m3/minの風量で空気を流通させたときの圧力を測定した。次に、作製した排ガス浄化用触媒(触媒層付きのハニカム基材)を用いて、リファレンスと同様に空気を流通させたときの圧力を測定した。そして、次式:〔(排ガス浄化用触媒の圧力−リファレンスの圧力)/リファレンスの圧力〕×100;から圧損増加率(%)を算出した。結果を図9に示す。なお、図9は、例Aの結果を「基準(1.000)」としたときの相対値で表している。この値が小さいほど圧損の上昇が小さく抑えられていることを表している。
A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcを、表4に示すように変更したこと以外は例Cと同様に、例E〜Iの排ガス浄化用触媒を作製した。また、各スラリーのコート量と、A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcとを例Gと同じように変更したこと以外は比較例1と同様にして、比較例4の排ガス浄化用触媒を作製した。比較例4と例E〜Iの触媒層の仕様を、表4にまとめる。
A部20a,B部20b,C部20cのコート量を表5に示すように変更したこと以外は例Gと同様に、例J〜Mの排ガス浄化用触媒を作製した。また、各スラリーのコート量と、A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcとを例Lと同じように変更したこと以外は比較例1と同様にして、比較例5の排ガス浄化用触媒を作製した。比較例5と例J〜Mの触媒層の仕様を、表5にまとめる。
A部20a,B部20b,C部20cのコート量を表6に示すように変更したこと以外は例Gと同様に、例N〜Rの排ガス浄化用触媒を作製した。また、各スラリーのコート量を表6に示すように変更し、かつ、A部20a,B部20b,C部20cのX方向のコート幅La,Lb,Lcを例Gと同様に変更したこと以外は比較例1と同様にして、比較例6の排ガス浄化用触媒を作製した。比較例6と例N〜Rの触媒層の仕様を、表6にまとめる。
Rhスラリーのコート量を95g/Lとし、Pdスラリーのコート量を120g/gとし、かつ、金属触媒を表7のように変更したこと以外は例Gと同様に、例S,Tの排ガス浄化用触媒を作製した。例S,Tの触媒層の仕様を、表7にまとめる。
上記した試験例(1)−1と同様に耐久試験を実施し、耐久試験終了後の排ガス浄化用触媒について高負荷時の排ガス浄化性能を評価した。具体的には、先ず、各例の排ガス浄化用触媒を排気量2.0Lのターボチャージャー付の自動車の排気経路に配置した。次に、WLTC(Worldwide harmonized Light duty Test Cycle)モードを走行し、高負荷領域(Ex−H、Phase4)におけるHC,CO,NOxの各成分の排出量(mg/mile)を測定した。
Rhスラリーのコート量を95g/Lとし、Pdスラリーのコート量を120g/gとし、かつ、金属触媒を表9のように変更したこと以外は例Gと同様に、例U,Vの排ガス浄化用触媒を作製した。
A部20a,B部20b,C部20cのコート量を表11に示すように変更したこと以外は例Gと同様に、例W,Xの排ガス浄化用触媒を作製した。
Claims (11)
- 内燃機関の排気経路に配置され、該内燃機関から排出される排ガスを浄化する排ガス浄化用触媒であって、
排ガス流入側の端部が開口した入側セルと、排ガス流出側の端部が開口した出側セルと、前記入側セルと前記出側セルとを仕切る多孔質な隔壁と、を有するウォールフロー構造の基材と、
前記基材に設けられ、金属触媒を含む触媒層と、
を備え、
前記触媒層は、
前記隔壁の内部に、前記排ガス流入側の端部から前記隔壁の延伸方向に沿って設けられているA部と、
前記隔壁の内部に、前記排ガス流出側の端部から前記隔壁の延伸方向に沿って設けられているC部と、
前記隔壁の延伸方向において前記A部と前記C部との間に配置され、前記隔壁の前記入側セルに接する側の表面と、前記隔壁の内部と、前記隔壁の前記出側セルに接する側の表面と、にわたって設けられているB部と、
を備える、排ガス浄化用触媒。 - 前記隔壁の延伸方向の全長を100%としたときに、
前記B部が、前記隔壁の全長の15%以上51%以下の長さで配置されている、
請求項1に記載の排ガス浄化用触媒。 - 前記隔壁の延伸方向の全長を100%としたときに、
前記A部が、前記隔壁の全長の10%以上40%以下の長さで配置されている、
請求項1または2に記載の排ガス浄化用触媒。 - 前記基材の体積1L当たりの前記B部のコート量が、145g/L以上である、
請求項1〜3の何れか一つに記載の排ガス浄化用触媒。 - 前記基材の体積1L当たりの前記C部のコート量が、前記基材の体積1L当たりの前記A部のコート量よりも多い、
請求項1〜4の何れか一つに記載の排ガス浄化用触媒。 - 前記基材の体積1L当たりの前記C部のコート量が、前記基材の体積1L当たりの前記A部のコート量よりも少ない、
請求項1〜4の何れか一つに記載の排ガス浄化用触媒。 - 前記A部が、ロジウムを含む、
請求項1〜6の何れか一つに記載の排ガス浄化用触媒。 - 前記B部が、前記隔壁の前記入側セルに接する側の表面に、ロジウムを含む、
請求項1〜7の何れか一つに記載の排ガス浄化用触媒。 - 前記C部が、ロジウムを含む、
請求項1〜8の何れか一つに記載の排ガス浄化用触媒。 - 前記A部が、パラジウムを含む、
請求項1〜9の何れか一つに記載の排ガス浄化用触媒。 - 前記内燃機関が、ガソリンエンジンである、
請求項1〜10の何れか一つに記載の排ガス浄化用触媒。
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JP6594163B2 (ja) * | 2015-10-30 | 2019-10-23 | 株式会社キャタラー | 排ガス浄化装置 |
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CN111050908B (zh) * | 2017-03-30 | 2023-04-21 | 庄信万丰股份有限公司 | 单块scr/asc/pna/doc紧密连接的催化剂 |
CN110582341B (zh) * | 2017-03-30 | 2023-02-10 | 庄信万丰股份有限公司 | 具有后部集中放热产生的asc/dec |
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2018
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- 2018-06-07 JP JP2018553161A patent/JP6445228B1/ja active Active
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- 2018-06-07 WO PCT/JP2018/021915 patent/WO2019012874A1/ja unknown
- 2018-06-07 CN CN201880046330.0A patent/CN110997141B/zh active Active
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JP6445228B1 (ja) | 2018-12-26 |
US11420189B2 (en) | 2022-08-23 |
CN110997141A (zh) | 2020-04-10 |
US20200129963A1 (en) | 2020-04-30 |
EP3636340B1 (en) | 2023-08-23 |
EP3636340A1 (en) | 2020-04-15 |
CN110997141B (zh) | 2023-09-26 |
WO2019012874A1 (ja) | 2019-01-17 |
EP3636340A4 (en) | 2020-07-08 |
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