WO2005063387A1 - Catalyseur de purification de gaz d'echappement - Google Patents

Catalyseur de purification de gaz d'echappement Download PDF

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Publication number
WO2005063387A1
WO2005063387A1 PCT/JP2004/018540 JP2004018540W WO2005063387A1 WO 2005063387 A1 WO2005063387 A1 WO 2005063387A1 JP 2004018540 W JP2004018540 W JP 2004018540W WO 2005063387 A1 WO2005063387 A1 WO 2005063387A1
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WO
WIPO (PCT)
Prior art keywords
transition metal
noble metal
metal compound
exhaust
purifying
Prior art date
Application number
PCT/JP2004/018540
Other languages
English (en)
Inventor
Masanori Nakamura
Hironori Wakamatsu
Katsuo Suga
Toru Sekiba
Original Assignee
Nissan Motor Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nissan Motor Co., Ltd. filed Critical Nissan Motor Co., Ltd.
Publication of WO2005063387A1 publication Critical patent/WO2005063387A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • 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
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • 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
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • transition metals have no catalytic activities in themselves, and it has been impossible to improve catalytic activities to decrease usage amounts of noble metals insofar as based on any of the conventional methods.
  • the present inventors have earnestly and repeatingly studied to solve the above-mentioned conventional techniques and the problems, and resultingly found such a unique phenomenon that exhaust-gas purifying performances are improved by a configuration in which a noble metal and a transition metal compound having a metallic portion are carried on the same porous carrier such that the noble metal and the transition metal compound are contacted with each other, thereby narrowly completing the present invention.
  • the catalytic activity is kept even when the noble metal is decreased in amount, by virtue of the coexistence of the noble metal and the transition metal compound which hardly exhibits a catalytic activity by itself, on the same porous carrier.
  • the reason of the above is considered to be based on occurrence of a phenomenon called "spillover" where hydrogen in exhaust gas is initially and dissociatively adsorbed onto a surface of the noble metal and then migrates to a surface of the transition metal compound to thereby reduce NOx on the surface of the transition metal compound under a so-called stoichiometric condition where an oxygen amount and a reductant amount in exhaust gas are identical in ratios.
  • the transition metal compound 3 is activated by virtue of spillover and acts as a catalytic site, thereby improving the catalytic activity.
  • This allows to obtain an effect that the catalytic activity of the noble metal is supplemented by the transition metal compound, thereby decreasing a usage amount of the noble metal.
  • the same effect as FIG. 1 can be obtained even in a state of another exhaust-gas purifying catalyst 11 shown in FIG. 2 which includes a noble metal 12 carried on a transition metal compound 13 which is in turn carried on a porous carrier 14.
  • the porous carrier include a porous substances such as alumina (aluminum oxide) and the like.
  • the catalytic activity is higher and the exhaust-gas purifying efficiency is improved, as compared with a state where the transition metal compound is oxide.
  • an interface between the porous carrier and the transition metal compound may form a complex oxide.
  • the transition metal element included in the transition metal compound and the noble metal, both contained in the exhaust-gas purifying catalyst are preferably 0.01 to 35 in weight ratio Bw/Aw therebetween. Weight ratios Bw/Aw less than 0.01 lead to the decreased number of contacted interfaces between the noble metal and transition metal compound, thereby making it difficult to obtain due catalytic activities, because the activation of the transition metal compound by virtue of spillover of the reducing gases (such as HC, H2, and CO) is insufficient then.
  • the reducing gases such as HC, H2, and CO
  • the amount of the noble metal is 0.5g or less per IL of exhaust-gas purifying catalyst. In this case, the effect of the decreased amount of the noble metal becomes more remarkable.
  • the porous carrier contains at least one kind of rare earth element selected from Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), and Nd (neodymium).
  • the obtained catalyst powder 50g of boehmite, and l,570g of 10% nitric-acid-containing aqueous solution were charged into an alumina-made porcelain pot, and shaken and ground together with alumina balls, thereby obtaining a catalyst slurry. Further, this catalyst slurry was loaded onto a honeycomb substrate made of cordierite (900 cell/2.5 mil) and an excessive slurry was removed by airflow, followed by drying at 120°C and firing thereafter at 400°C in airflow, thereby coating the catalyst powder onto the honeycomb substrate to obtain an intended exhaust-gas purifying catalyst.
  • the numerical value accompanied by the unit "cell” represents the number of cells per 1 inch (about 2.54cm) square of honeycomb.
  • Example 9 Impregnated by immersion into a ⁇ -alumina as a porous carrier was an aqueous mixture solution of a dinitro-diamine Pt nitric acid-acidic aqueous solution and a Co(II) nitrate hexahydrate such that Pt was 0.5% and Co was 10.0% when calculated as elements, respectively, and then it was dried at 150°Cx20 hours, followed by firing at 400°Cxl hour in airflow. Thereafter, the same procedure as Example 1 was conducted, to obtain a specimen of Example 9.
  • Example 12 Impregnated by immersion into a ⁇ -alumina as a porous carrier was an aqueous mixture solution of an Au chloride aqueous acidic solution and an Ni(II) nitrate hexahydrate such that Au was 0.5% and Ni was 10.0% when calculated as elements, respectively, and then it was dried at 150°Cx20 hours, followed by firing at 400°Cxl hour in airflow. Thereafter, the same procedure as Example 1 was conducted, to obtain a specimen of Example 12. (Example 13) Impregnated into a ⁇ -alumina as a porous carrier carrying 3% of
  • Measurement was conducted by fixing the specimen on an indium foil while adopting a complex-type surface analyzing apparatus manufactured by PHI, under the condition that the X-ray source was Al-K ⁇ ray (1486.6eV, 300W), the photoelectron extraction angle was 45° (measurement depth of 4nm), and the measuring area was 2mmx0.8mm.
  • hydrogen hydrogen 0.2%/nitrogen
  • Example 4 the catalyst amount coated on the obtained honeycomb substrate was llOg per IL of honeycomb substrate, the carried concentration of noble metal (Pt) was 0.7%, the carried concentration of transition metal element Co was 10.0%, the weight Aw of noble metal (Pt) per IL of honeycomb substrate was 0.7g, the weight Bw of transition metal element Co included in transition metal compound was lO.Og, and Bw/Aw was 14.3. Further, the particle diameter Ar of noble metal (Pt) was 4.9nm, the particle diameter Br of transition metal element Co included in transition metal compound was 83nm, Br/Ar was 16.9, B(0)/B(X) was 8.3, and the purifying ratio after durability test was 58%.
  • Example 6 the catalyst amount coated on the obtained honeycomb substrate was llOg per IL of honeycomb substrate, the carried concentration of noble metal (Rh) was 0.3%, the carried concentration of transition metal element Fe was 5.0%, the weight Aw of noble metal (Rh) per IL of honeycomb substrate was 0.3g, the weight Bw of transition metal element Fe included in transition metal compound was 5.0g, and Bw/Aw was 16.7. Further, the particle diameter Ar of noble metal (Pt) was 2.8nm, the particle diameter Br of transition metal element Fe included in transition metal compound was 96nm, Br/Ar was 34.3, B(0)/B(X) was 6.3, and the purifying ratio after durability test was 73%.
  • Example 13 the catalyst amount coated on the obtained honeycomb substrate was llOg per IL of honeycomb substrate, the carried concentration of noble metal (Pt) was 0.3%, the carried concentration of transition metal element Ni was 5.0%, the carried concentration of rare earth element Y was 6.7% when calculated as oxide, the weight Aw of noble metal (Pt) per IL of honeycomb substrate was 0.3g, the weight Bw of transition metal element Ni included in transition metal compound was 5.0g, the weight Cw of rare earth element Y was 6.7g, Bw/Aw was 16.7, and Cw/Bw was 1.3. Further, the particle diameter Ar of noble metal (Pt) was 5.0nm, the particle diameter Br of transition metal element Ni included in transition metal compound was 43nm, and Br/Ar was 8.6.
  • the catalyst amount coated on the obtained honeycomb substrate was 220g per IL of honeycomb substrate, the carried concentration of noble metal (Pt) was 0.3%, the carried concentration of transition metal element Co was ⁇ .0%, the weight Aw of noble metal (Pt) per IL of honeycomb substrate was 0.3g, the weight Bw of transition metal element Co included in transition metal compound was ⁇ .Og, and Bw/Aw was 16.7. B(0)/B(X) was 0.6, and the purifying ratio after durability test was 10%.

Abstract

La présente invention concerne un catalyseur de purification de gaz d'échappement qui comprend: au moins un type de métal noble sélectionné parmi Ru, Rh, Pd, Ag, Ir, Pt, et Au, un composé métal de transition comprenant au moins un éléments métal de transition sélectionnée parmi Mn, Fe, Co, Ni, Cu, et Zn, ce composé métal de transition possédant une partie métallique et, un porteur poreux portant ce métal noble et ce composé métal de transition.
PCT/JP2004/018540 2003-12-25 2004-12-07 Catalyseur de purification de gaz d'echappement WO2005063387A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-430737 2003-12-25
JP2003430737A JP2005185959A (ja) 2003-12-25 2003-12-25 排ガス浄化用触媒

Publications (1)

Publication Number Publication Date
WO2005063387A1 true WO2005063387A1 (fr) 2005-07-14

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WO (1) WO2005063387A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1720654A1 (fr) * 2004-02-24 2006-11-15 Nissan Motor Company, Limited Poudre de catalyseur, catalyseur de purification de gaz dechappement et procede de production de la poudre de catalyseur
US9358527B2 (en) 2012-07-09 2016-06-07 Toyota Jidosha Kabushiki Kaisha Exhaust gas purification catalyst and production method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012035182A (ja) * 2010-08-05 2012-02-23 Daihatsu Motor Co Ltd 触媒組成物
WO2012108061A1 (fr) * 2011-02-07 2012-08-16 Toyota Jidosha Kabushiki Kaisha Catalyseur de purification de nox
KR101614816B1 (ko) * 2011-05-24 2016-04-22 도요타 지도샤（주） 배기 정화 시스템
JP2015157236A (ja) * 2014-02-21 2015-09-03 マツダ株式会社 エンジン排ガス浄化用触媒材及びパティキュレートフィルタ

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867309A (en) * 1972-08-24 1975-02-18 Mobil Oil Corp Catalyst composition for removing noxious components from a gaseous stream
US4504598A (en) * 1983-05-12 1985-03-12 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for producing honeycomb catalyst for exhaust gas conversion
EP0304095A2 (fr) * 1984-06-14 1989-02-22 Engelhard Corporation Catalyseur pour le traitement des gaz d'échappement
EP0306945A1 (fr) * 1987-09-08 1989-03-15 Phillips Petroleum Company Oxydation de l'oxyde de carbone et catalysateur ainsi utilisé
EP0449423A1 (fr) * 1990-02-26 1991-10-02 Nippon Shokubai Co., Ltd. Catalyseur pour la purification de gaz d'échappement de moteurs diesel
US5756057A (en) * 1993-04-28 1998-05-26 Nippon Shokubai Co., Ltd. Method for removal of nitrogen oxides from exhaust gas
US6245307B1 (en) * 1994-06-17 2001-06-12 Ict Co., Ltd. Catalyst for purifying exhaust gas from lean burn engine and method for purification

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867309A (en) * 1972-08-24 1975-02-18 Mobil Oil Corp Catalyst composition for removing noxious components from a gaseous stream
US4504598A (en) * 1983-05-12 1985-03-12 Nippon Shokubai Kagaku Kogyo Co., Ltd. Process for producing honeycomb catalyst for exhaust gas conversion
EP0304095A2 (fr) * 1984-06-14 1989-02-22 Engelhard Corporation Catalyseur pour le traitement des gaz d'échappement
EP0306945A1 (fr) * 1987-09-08 1989-03-15 Phillips Petroleum Company Oxydation de l'oxyde de carbone et catalysateur ainsi utilisé
EP0449423A1 (fr) * 1990-02-26 1991-10-02 Nippon Shokubai Co., Ltd. Catalyseur pour la purification de gaz d'échappement de moteurs diesel
US5756057A (en) * 1993-04-28 1998-05-26 Nippon Shokubai Co., Ltd. Method for removal of nitrogen oxides from exhaust gas
US6245307B1 (en) * 1994-06-17 2001-06-12 Ict Co., Ltd. Catalyst for purifying exhaust gas from lean burn engine and method for purification

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1720654A1 (fr) * 2004-02-24 2006-11-15 Nissan Motor Company, Limited Poudre de catalyseur, catalyseur de purification de gaz dechappement et procede de production de la poudre de catalyseur
US9358527B2 (en) 2012-07-09 2016-06-07 Toyota Jidosha Kabushiki Kaisha Exhaust gas purification catalyst and production method thereof

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