WO2010096612A2 - Aging-resistant catalyst article for internal combustion engines - Google Patents

Aging-resistant catalyst article for internal combustion engines Download PDF

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Publication number
WO2010096612A2
WO2010096612A2 PCT/US2010/024659 US2010024659W WO2010096612A2 WO 2010096612 A2 WO2010096612 A2 WO 2010096612A2 US 2010024659 W US2010024659 W US 2010024659W WO 2010096612 A2 WO2010096612 A2 WO 2010096612A2
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Prior art keywords
impregnated
palladium
layer
platinum
catalytic layer
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PCT/US2010/024659
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English (en)
French (fr)
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WO2010096612A3 (en
Inventor
Xinsheng Liu
Ye Liu
Pascaline Harrison Tran
Michael P. Galligan
Wenyong Lin
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BASF Catalysts LLC
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BASF Catalysts LLC
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Priority to JP2011551235A priority Critical patent/JP5499053B2/ja
Priority to KR1020117021767A priority patent/KR101710979B1/ko
Priority to EP10744333.5A priority patent/EP2398586B1/en
Priority to CN201080017048.3A priority patent/CN102405103B/zh
Priority to BRPI1008389-8A priority patent/BRPI1008389B1/pt
Publication of WO2010096612A2 publication Critical patent/WO2010096612A2/en
Publication of WO2010096612A3 publication Critical patent/WO2010096612A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B01J35/57—Honeycombs
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • 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
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • 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
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • 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
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/908—O2-storage component incorporated in the 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
    • 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
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • 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
    • F01N2590/00—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines
    • F01N2590/06—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines for hand-held tools or portables devices
    • 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
    • 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

  • the platinum group metals in the TWC catalysts are typically disposed on a high surface area, refractory metal oxide support, e.g., a high surface area alumina coating, or on an oxygen storage component.
  • Fig. 1 is a bar graph showing the results of Example 2, comparing NOx emissions for a conventional catalyst and a catalyst according to the invention in different drive cycles.
  • Zirconia-coated alumina for use in the present invention as a support for rhodium in the second catalytic layer may be prepared according any of the methods known in the art. These include, for example, introduction of zirconium w-propoxide in /7-pro ⁇ anol to a calcined alumina support as described by S. Damyanova, et al. Journal of Catalysis 168, 421-430 (1997), or impregnation of alumina powder using a nitric acid solution of zirconium hydroxide as described by M.M.V.M. Souza, et al. Phys. Stat. Sol. (a) 187, No. 1, 297-303 (2001).
  • One aspect of the invention provides a catalyst article comprising: a catalytic material on a substrate, the catalytic material comprising the two catalytic layers described herein and the catalyst article further comprising an etch coat layer between the substrate and the first catalytic layer.
  • the etch coat layer comprises a high surface area refractory metal oxide and is preferably prepared such that the surface is substantially uniform.
  • a substantially uniform surface on the etch coat provides improved bonding of the first catalytic layer to the substrate and is particularly advantageous when the catalyst article is used in high-vibration environments such as small engines.
  • Fast and thorough drying of the etch coat facilitates production of the substantially uniform surface and may be achieved by drying the layer at lower temperatures under moving air. Thorough drying of the etch coat also contributes to achievement of an even distribution of the palladium component in the first catalytic layer.
  • significant improvement in the reduction of NOx emissions from a small gasoline engine can be obtained using the catalyst articles of the invention. Improvement in hydrocarbon and carbon monoxide emissions may also be achieved.
  • the catalyst articles of the invention also exhibit substantially improved performance in sequential lean-rich aging test protocols.
  • a detailed embodiment provides two catalytic layers on the substrate.
  • a first catalytic layer is a high-palladium layer coated on the substrate and comprises palladium impregnated on praseodymia-doped zirconia and alumina ⁇ and platinum impregnated on alumina.
  • the first catalytic layer is coated on the substrate and calcined.
  • a second catalytic layer is coated on the first catalytic layer and comprises rhodium impregnated on zirconia-coated alumina and platinum impregnated on a ceria-zirconia composite.
  • the second catalytic layer is also calcined.
  • the first catalytic layer comprises a ceria-free OSC support, e.g., praseodymia-doped zirconia, and a high surface area refractory metal oxide such as gamma alumina impregnated with palladium and palladium/platinum, respectively.
  • a second catalytic layer coated on the first catalytic layer comprises platinum and/or rhodium but does not contain palladium.
  • the second catalytic layer comprises rhodium impregnated on a zirconia-coated alumina support and platinum impregnated on a ceria-zirconia composite oxide support.
  • a gentle to moderate airflow is maintained across the substrate during the drying of the etch coat, as may be provided by a conventional fan.
  • the airflow may be provided by any suitable means, and will be determined by the size and/or configuration of the drying furnace.
  • the etch coat layer is then calcined, typically at 490-550° C for 1-2 hrs.
  • the desired surface uniformity is determined by visual or microscopic methods, such as direct visualization by light microscopy, scanning electron micrographs, metallography, and the like.
  • the etch coat is preferably thin, for example less than 10 ⁇ m in thickness.
  • the etch coat is 1-8 ⁇ m in thickness, 1-5 ⁇ m in thickness, 1-3 ⁇ m in thickness or about 1 ⁇ m in thickness.
  • a thin etch coat and a substantially uniform etch coat surface increase adherence of the catalytic layers to the etch coat and to the substrate.
  • the first catalytic layer is coated on the etch coat.
  • the first catalytic layer coating is accomplished by depositing on the etch coat a high-palladium catalytic material comprising palladium impregnated on a ceria-free, rare earth- doped zirconia support and platinum impregnated on a refractory metal oxide support.
  • the first catalytic layer is then dried and calcined, typically at 490-550°C for 1-2 hrs.
  • a second catalytic layer is coated on the first catalytic layer.
  • the second catalytic layer comprises platinum impregnated on a refractory metal oxide support and rhodium impregnated on a zirconia-coated or yttria-coated alumina support, and does not contain palladium.
  • the rare earth component of the OSC in the first catalytic layer may be 1-40% by weight of the composite.
  • the OSC in the second catalytic layer may be, for example, ceria-zirconia.
  • the ratio of PGM content of the catalyst article is typically 0.5-10 /1-80/0.5-10, 1-5/2-10/1-5. 1-5/20-60/1-5 or about 1/40/2.4 by weight (Pt/Pd/Rh).
  • the substrate may be any of the materials typically used for preparing TWC catalysts and will preferably comprise a metal or ceramic structure.
  • Any suitable substrate may be employed, such as a monolithic substrate of the type having a plurality of fine, parallel gas flow passages extending therethrough from an inlet or an outlet face of the substrate, such that passages are open to fluid flow therethrough.
  • the passages which are essentially straight paths from their fluid inlet to their fluid outlet, are defined by walls on which the catalytic material is coated as a "washcoat" so that the gases flowing through the passages contact the catalytic material.
  • the flow passages of the monolithic substrate are thin- walled channels which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures may contain from about 60 to about 600 or more gas inlet openings (i.e., "cells") per square inch of cross section.
  • the substrates useful for the layered catalyst composites of the present invention may also be metallic in nature and be composed of one or more metals or metal alloys.
  • the metallic substrates may be employed in various shapes such as corrugated sheet, metal plate, wire mesh or monolithic form.
  • Preferred metallic supports include the heat resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component.
  • Such alloys may contain one or more of nickel, chromium and/or aluminum, and the total amount of these metals may advantageously comprise at least 15 wt. % of the alloy, e.g., 10-25 wt. % of chromium, 3-8 wt. % of aluminum and up to 20 wt. % of nickel.
  • platinum group metals e.g., palladium, rhodium, platinum, and/or combinations of the same
  • stabilizers and/or promoters such components may be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes.
  • the coated substrate is calcined by heating, e.g., at 500-600°C for about 1 to about 3 hours.
  • the PGM component is utilized in the form of a compound or complex to achieve dispersion of the component on the refractory metal oxide support.
  • a suitable method of preparing any catalytic layer of the catalyst article of the invention is to prepare a mixture of a solution of a desired platinum group metal component and at least one support, such as a finely divided, high surface area, refractory metal oxide support, e.g., gamma alumina or zirconia-coated alumina, which is sufficiently dry to absorb substantially all of the solution to form a wet solid which is later combined with water to form a coatable slurry.
  • the slurry is acidic, having, for example, a pH of about 2 to less than about 7. The pH of the slurry may be lowered by the addition of an adequate amount of an inorganic or an organic acid to the slurry.
  • Inorganic acids include, but are not limited to, nitric acid.
  • Organic acids include, but are not limited to, acetic, propionic, oxalic, malonic, succinic, glutamic, adipic, maleic, fumaric, phthalic, tartaric, citric acid and the like.
  • water-soluble or water-dispersible compounds of oxygen storage components e.g., cerium-zirconium composite, a stabilizer, e.g., barium acetate, and a promoter, e.g., lanthanum nitrate, may be added to the slurry.
  • Platinum group metal components may also be impregnated in the oxygen storage component, e.g., ceria-zirconia or praseodymia-doped zirconia, in a similar manner prior to addition to the slurry.
  • Example 1 A catalyst was prepared in the following manner.
  • a middle layer i.e., the first catalytic layer in the form of an aqueous solution was then applied to the surface of the carrier coated with the undercoat,
  • the slurry used for the middle layer consisted of an approximately 40 % solid content, aqueous solution containing 225 g of alumina, 228 g of Pr-doped zirconia, 3Og of barium hydroxide, 12.2g of Pd impregnated on alumina and Pd-doped zirconia as Pd nitrate solution and 0.06g of Pt impregnated as Pt nitrate solution.
  • the coated carrier was then calcined at 550° C for 1 hour to obtain a dried washcoat at approximately 1.64 g/in 3 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
PCT/US2010/024659 2009-02-20 2010-02-19 Aging-resistant catalyst article for internal combustion engines Ceased WO2010096612A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2011551235A JP5499053B2 (ja) 2009-02-20 2010-02-19 内燃エンジン用耐老化性触媒物品
KR1020117021767A KR101710979B1 (ko) 2009-02-20 2010-02-19 내연 기관을 위한 에이징-내성 촉매 물품
EP10744333.5A EP2398586B1 (en) 2009-02-20 2010-02-19 Aging-resistant catalyst article for internal combustion engines
CN201080017048.3A CN102405103B (zh) 2009-02-20 2010-02-19 用于内燃机的抗老化催化剂制品
BRPI1008389-8A BRPI1008389B1 (pt) 2009-02-20 2010-02-19 Artigo catalisador, e, métodos para tratar escapamento de motor e para fabricar um artigo catalisador

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15405309P 2009-02-20 2009-02-20
US61/154,053 2009-02-20
US12/706,742 2010-02-17
US12/706,742 US10773209B2 (en) 2009-02-20 2010-02-17 Aging-resistant catalyst article for internal combustion engines

Publications (2)

Publication Number Publication Date
WO2010096612A2 true WO2010096612A2 (en) 2010-08-26
WO2010096612A3 WO2010096612A3 (en) 2010-12-23

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CN102405103A (zh) 2012-04-04
WO2010096612A3 (en) 2010-12-23
JP5499053B2 (ja) 2014-05-21
KR20110122194A (ko) 2011-11-09
CN102405103B (zh) 2016-01-13
US10773209B2 (en) 2020-09-15
EP2398586B1 (en) 2015-12-02
KR101710979B1 (ko) 2017-03-02
EP2398586A2 (en) 2011-12-28
EP2398586A4 (en) 2012-11-14
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JP2012520163A (ja) 2012-09-06
BRPI1008389B1 (pt) 2021-06-22

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