JP3843102B2 - 排ガス浄化触媒及びその製造方法、並びに排ガス浄化触媒装置 - Google Patents
排ガス浄化触媒及びその製造方法、並びに排ガス浄化触媒装置 Download PDFInfo
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- JP3843102B2 JP3843102B2 JP2004002667A JP2004002667A JP3843102B2 JP 3843102 B2 JP3843102 B2 JP 3843102B2 JP 2004002667 A JP2004002667 A JP 2004002667A JP 2004002667 A JP2004002667 A JP 2004002667A JP 3843102 B2 JP3843102 B2 JP 3843102B2
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- JP
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- Prior art keywords
- exhaust gas
- gas purification
- purification catalyst
- acid
- carboxylic acid
- 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.)
- Expired - Fee Related
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
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Classifications
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
<実施例1〜3>
[担持用担体複合酸化物の作製]
所定量の硝酸ランタン六水和物、及び硝酸アルミニウム九水和物をイオン交換水に溶解し、混合水溶液を作製した。次に、所定量のリンゴ酸をイオン交換水に溶解し、リンゴ酸水溶液を作製した。この二つの水溶液を混合して、ホットプレートスターラにのせ、250℃で撹拌子を用いて撹拌しながら加熱し、水分蒸発の後、分解乾固させ、乾固物を乳鉢で粉砕した。これをアルミナ坩堝に移し、マッフル炉にて2.5℃/minで350℃まで昇温し、350℃で3時間熱処理を施した。これにより、リンゴ酸塩、硝酸根を除去した仮焼成体を作製した。仮焼成体を乳鉢で15分間粉砕混合した後、再びアルミナ坩堝に入れ、マッフル炉にて5℃/minで800℃まで昇温し、800℃で10時間熱処理を施した。これにより、LaAlO3なる組成のペロブスカイト複合酸化物を作製した。また、同様に、PrAlO3及びNdAlO3なる組成のペロブスカイト複合酸化物を作製した。
次に、所定量の硝酸パラジウムニ水和物をイオン交換水に溶解させ、硝酸パラジウム水溶液を作製した。硝酸パラジウム水溶液と所定量のLaAlO3、PrAlO3又はNdAlO3粉末とをナス型フラスコに入れ、ナス型フラスコをロータリーエバポレータで減圧しながら、60℃の湯浴中で蒸発乾固させた。その後、マッフル炉にて2.5℃/minで250℃まで昇温し、さらに5℃/minで750℃まで昇温して、750℃で3時間保持した。これにより、PdOを上記各ペロブスカイト複合酸化物に含浸担持したPd/LaAlO3、Pd/PrAlO3及びPd/NdAlO3なる実施例1〜3の触媒粉末を得た。これらの触媒粉末についての比表面積を表1に示す。
次に、得られた触媒粉末について、初期及び耐久処理後の活性評価を実施した。評価は、自動車のモデル排ガスを触媒に流通させ、A/F(空燃比)=14.6相当、SV(流量)=50000h−1にて行った。耐久処理は、A/F=14.6相当のモデル排ガスにより900℃の耐久温度で20時間行った。これらの結果を表2,3に示す。すなわち、表2には、触媒の昇温試験における、CO、HC、NOの50%浄化温度を示す。また、表3には、耐久処理後の触媒の昇温試験における、CO、HC、NOの50%浄化温度を示す。
実施例1と同様の方法でPd/Al2O3を製造し、各種活性評価を行った。耐久温度は900℃とした。その結果を表1〜3に併記する。
実施例1と同様の方法でPd/GdAlO3を製造した。なお、GdAlO3は斜方晶である。この触媒について、各種活性評価を行った。耐久温度は900℃とした。その結果を表1〜3に併記する。
実施例1と同様の方法でPd/LaNiO3を製造した。なお、LaNiO3は三方晶又は菱面体晶である。この触媒について、各種活性評価を行った。耐久温度は800℃とした。その結果を表1〜3に併記する。
実施例1と同様の方法でPd/LaMnO3を製造した。なお、LaMnO3は斜方晶である。この触媒について、各種活性評価を行った。耐久温度は800℃とした。その結果を表1〜3に併記する。
実施例1と同様の方法でPd/LaCoO3を製造した。なお、LaCoO3は斜方晶である。この触媒について、各種活性評価を行った。耐久温度は800℃とした。その結果を表1〜3に併記する。
実施例1と同様の方法でPd/LaFeO3を製造した。なお、LaFeO3は斜方晶である。この触媒について、各種活性評価を行った。耐久温度は900℃とした。その結果を表1〜3に併記する。
所定量の酸化ランタン、酸化アルミニウムをめのう乳鉢で混合し、アルミナ坩堝に入れ、マッフル炉にて1100℃で10時間焼成し、固相反応法によりLaAlO3を作製した。これを用い、実施例1のと同様の方法で貴金属を担持し、Pd/LaAlO3を製造した。この触媒について、各種活性評価を行った。耐久温度は900℃とした。その結果を表1〜3に併記する。
Claims (10)
- PdおよびPdOがAl酸化物に担持されている排ガス浄化触媒において、
前記Al酸化物が単相のLnAlO3(Ln:希土類金属)であるとともにその結晶系が三方晶又は菱面体晶であることを特徴とする排ガス浄化触媒。 - 触媒粉末の比表面積が8m 2 /g以上であることを特徴とする請求項1に記載の排ガス浄化触媒。
- 化合物群(OH基又はSH基を有する炭素数2〜20のカルボン酸、炭素数2又は3のジカルボン酸、及び炭素数1〜20のモノカルボン酸)から選ばれた少なくとも1種を前記LnとAlの硝酸塩水溶液へ添加する工程を経て製造されたことを特徴とする請求項1又は2に記載の排ガス浄化触媒。
- 前記硝酸塩水溶液を蒸発乾固させて、カルボン酸錯体重合物を作製する工程と、前記カルボン酸錯体重合物を焼成する焼成工程とを経て製造されたことを特徴とする請求項3に記載の排ガス浄化触媒。
- 前記カルボン酸はリンゴ酸であることを特徴とする請求項3または4に記載の排ガス浄化触媒。
- LnAlO3(Ln:希土類金属)上にPdが担持された排ガス浄化触媒であって、前記Pdが担持された表面領域では、PdがPd2+の状態で存在していることを特徴とする請求項2〜5のいずれかに記載の排ガス浄化触媒。
- PdおよびPdOがAl酸化物に担持されている排ガス浄化触媒を製造するにあたり、前記Al酸化物が単相のLnAlO 3 (Ln:希土類金属)であるとともにその結晶系が三方晶又は菱面体晶であり、
化合物群(OH基又はSH基を有する炭素数2〜20のカルボン酸、炭素数2又は3のジカルボン酸、及び炭素数1〜20のモノカルボン酸)から選ばれた少なくとも1種を前記LnとAlの硝酸塩水溶液へ添加する工程を含むことを特徴とする排ガス浄化触媒の製造方法。 - 前記硝酸塩水溶液を蒸発乾固させて、カルボン酸錯体重合物を作製する工程と、
前記カルボン酸錯体重合物を焼成する焼成工程とを含むことを特徴とする請求項7に記載の排ガス浄化触媒の製造方法。 - 前記焼成工程における焼成温度が、1000℃以下であることを特徴とする請求項8に記載の排ガス浄化触媒の製造方法。
- 請求項1〜5のいずれかに記載の排ガス浄化触媒を用いた排ガス浄化触媒装置。
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JP2004002667A JP3843102B2 (ja) | 2003-08-06 | 2004-01-08 | 排ガス浄化触媒及びその製造方法、並びに排ガス浄化触媒装置 |
RU2006106714/04A RU2316395C2 (ru) | 2003-08-06 | 2004-05-27 | Катализатор очистки выхлопного газа, способ его получения и оборудование катализатора очистки выхлопного газа |
KR1020067002449A KR100738866B1 (ko) | 2003-08-06 | 2004-05-27 | 배기 가스 정화 촉매와 그 제조 방법 및 배기 가스 정화촉매 장치 |
EP04745369.1A EP1661619B1 (en) | 2003-08-06 | 2004-05-27 | Method for the production of an exhaust gas clarifying catalyst |
CA2534278A CA2534278C (en) | 2003-08-06 | 2004-05-27 | Purification catalyst for exhaust gas, production method therefor, and purification catalyst equipment for exhaust gas |
PCT/JP2004/007263 WO2005014166A1 (ja) | 2003-08-06 | 2004-05-27 | 排ガス浄化触媒及びその製造方法、並びに排ガス浄化触媒装置 |
US10/567,341 US7585809B2 (en) | 2003-08-06 | 2004-05-27 | Purification catalyst for exhaust gas, production method therefor, and purification catalyst equipment for exhaust gas |
BRPI0413351A BRPI0413351B8 (pt) | 2003-08-06 | 2004-05-27 | método para produção de um catalisador para purificação de gás de exaustão, compreendendo um lnalo3 (ln: la, pr ou nd) suportando pd |
MYPI20042886A MY145043A (en) | 2003-08-06 | 2004-07-19 | Purification catalyst for exhaust gas, production method therefor, and purification catalyst equipment for exhaust gas |
TW093121647A TWI243710B (en) | 2003-08-06 | 2004-07-20 | Purification catalyst for exhaust gas, production method therefor, and purification catalyst equipment for exhaust gas |
US12/324,005 US20090131250A1 (en) | 2003-08-06 | 2008-11-26 | Purification catalyst for exhaust gas, production method therefor, and purification catalyst equipment for exhaust gas |
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CN101027126A (zh) | 2004-09-24 | 2007-08-29 | 本田技研工业株式会社 | 排气净化用催化剂和排气净化装置 |
US7704486B2 (en) * | 2005-02-16 | 2010-04-27 | Basf Corporation | Precious metal water-gas shift catalyst with oxide support modified with rare earth elements |
JP4325648B2 (ja) * | 2005-10-24 | 2009-09-02 | トヨタ自動車株式会社 | 触媒担体及び排ガス浄化用触媒 |
WO2007114082A1 (ja) * | 2006-03-30 | 2007-10-11 | Ict Co., Ltd. | 内燃機関排気ガスの浄化方法 |
US8377400B2 (en) * | 2008-10-03 | 2013-02-19 | GM Global Technology Operations LLC | Methods and systems for oxidizing nitric oxide in a gas stream |
EP2452750B1 (en) * | 2009-07-09 | 2018-03-21 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst and method for producing same |
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EP0130835B1 (en) * | 1983-07-01 | 1990-05-02 | Hitachi, Ltd. | High temperature stable catalyst, process for preparing same and process for conducting chemical reaction using same |
JPS62269747A (ja) | 1986-05-19 | 1987-11-24 | Toyota Central Res & Dev Lab Inc | 排ガス浄化用触媒 |
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CN1021412C (zh) | 1988-10-26 | 1993-06-30 | 中国科学院生态环境研究中心 | 含贵金属的稀土复合氧化物型蜂窝催化剂及其制法 |
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US6060420A (en) | 1994-10-04 | 2000-05-09 | Nissan Motor Co., Ltd. | Composite oxides of A-site defect type perovskite structure as catalysts |
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KR100738866B1 (ko) | 2007-07-16 |
KR20060034722A (ko) | 2006-04-24 |
TW200512041A (en) | 2005-04-01 |
BRPI0413351B8 (pt) | 2016-09-13 |
BRPI0413351B1 (pt) | 2015-02-24 |
CA2534278A1 (en) | 2005-02-17 |
EP1661619A1 (en) | 2006-05-31 |
US20090131250A1 (en) | 2009-05-21 |
CA2534278C (en) | 2010-03-30 |
RU2006106714A (ru) | 2006-08-10 |
JP2005066587A (ja) | 2005-03-17 |
US20090005241A1 (en) | 2009-01-01 |
EP1661619A4 (en) | 2010-01-20 |
TWI243710B (en) | 2005-11-21 |
MY145043A (en) | 2011-12-15 |
EP1661619B1 (en) | 2014-07-02 |
WO2005014166A1 (ja) | 2005-02-17 |
US7585809B2 (en) | 2009-09-08 |
BRPI0413351A (pt) | 2006-10-10 |
RU2316395C2 (ru) | 2008-02-10 |
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