US20080120970A1 - NOx Storage Materials and Traps Resistant to Thermal Aging - Google Patents

NOx Storage Materials and Traps Resistant to Thermal Aging Download PDF

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Publication number
US20080120970A1
US20080120970A1 US11/564,494 US56449406A US2008120970A1 US 20080120970 A1 US20080120970 A1 US 20080120970A1 US 56449406 A US56449406 A US 56449406A US 2008120970 A1 US2008120970 A1 US 2008120970A1
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Prior art keywords
oxide
particles
ceria
catalyst
ceria particles
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US11/564,494
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Marcus Hilgendorff
Stanley Roth
Susanne Stiebels
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BASF Catalysts LLC
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BASF Catalysts LLC
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Priority to US11/564,494 priority Critical patent/US20080120970A1/en
Assigned to BASF CATALYSTS LLC reassignment BASF CATALYSTS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HILGENDORFF, MARCUS, STIEBELS, SUSANNE, ROTH, STANLEY
Priority to BRPI0719512A priority patent/BRPI0719512B1/pt
Priority to MX2009005675A priority patent/MX2009005675A/es
Priority to ES13172000.5T priority patent/ES2650736T3/es
Priority to DE202007019526U priority patent/DE202007019526U1/de
Priority to DE202007019493U priority patent/DE202007019493U1/de
Priority to CA2671020A priority patent/CA2671020C/en
Priority to EP13172000.5A priority patent/EP2644271B1/en
Priority to EP07854809.6A priority patent/EP2104567B2/en
Priority to EP17179750.9A priority patent/EP3257582A1/en
Priority to KR1020097013366A priority patent/KR101391005B1/ko
Priority to PCT/US2007/085759 priority patent/WO2008067375A1/en
Priority to ES07854809.6T priority patent/ES2458499T5/es
Priority to JP2009539458A priority patent/JP2010510884A/ja
Priority to RU2009124599/04A priority patent/RU2009124599A/ru
Priority to CN200780050588XA priority patent/CN101610844B/zh
Priority to ARP070105314A priority patent/AR064038A1/es
Publication of US20080120970A1 publication Critical patent/US20080120970A1/en
Priority to ZA200904435A priority patent/ZA200904435B/xx
Priority to US12/497,846 priority patent/US8022010B2/en
Priority to US13/272,007 priority patent/US8592337B2/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • 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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
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    • B01D—SEPARATION
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    • B01D2255/204—Alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • 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
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/91—NOx-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
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    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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

  • Embodiments of the invention relate nitrogen oxide storage materials and methods for their manufacture. More particularly, embodiments of the invention pertain to NO x storage materials that are resistant to thermal aging and methods of making such materials.
  • the nitrogen oxide storage materials may be part of a catalytic trap used to treat exhaust gas streams, especially those emanating from lean-burn gasoline or diesel engines.
  • NO x nitrogen oxides
  • Conventional three-way conversion (“TWC”) automotive catalysts are suitable for abating NO x , carbon monoxide a (“CO”) and hydrocarbon (“HC”) pollutants in the exhaust of engines operated at or near stoichiometric air/fuel conditions.
  • CO carbon monoxide a
  • HC hydrocarbon
  • An air-to-fuel (“A/F”) ratio of 14.65:1 (weight of air to weight of fuel) is the stoichiometric ratio corresponding to the combustion of a hydrocarbon fuel, such as gasoline, with an average formula CH 1.88 .
  • Engines are being designed to operate under lean conditions as a fuel economy measure.
  • Such future engines are referred to as “lean-burn engines”. That is, the ratio of air to fuel in the combustion mixtures supplied to such engines is maintained considerably above the stoichiometric ratio (e.g., at an air-to-fuel weight ratio of 18:1) so that the resulting exhaust gases are “lean”, i.e., the exhaust gases are relatively high in oxygen content.
  • lean-burn engines provide enhanced fuel economy, they have the disadvantage that conventional TWC catalysts are not effective for reducing NO x emissions from such engines because of excessive oxygen in the exhaust.
  • Attempts to overcome this problem have included operating lean-burn engines with brief periods of fuel-rich operation (engines which operate in this fashion are sometimes referred to as “partial lean-burn engines”).
  • the exhaust of such engines is treated with a catalyst/NO x sorbent which stores NO x during periods of lean (oxygen-rich) operation, and releases the stored NO x during the rich (fuel-rich) periods of operation.
  • the catalyst component of the catalyst/NO x sorbent promotes the reduction of NO x to nitrogen by reaction of NO x (including NO x released from the NO x sorbent) with HC, CO and/or hydrogen present in the exhaust.
  • Diesel engines provide better fuel economy than gasoline engines and normally operate 100% of the time under lean conditions, where the reduction of NOx is difficult due to the presence of excess oxygen.
  • the catalyst/NOx sorbent is effective for storing NOx.
  • a transient rich condition must be utilized to release/reduce the stored NOx to nitrogen.
  • this transient reducing condition will require unique engine calibration or injection of a diesel fuel into the exhaust to create the next reducing environment.
  • NO x storage (sorbent) components including alkaline earth metal oxides, such as oxides of Mg, Ca, Sr and Ba, alkali metal oxides such as oxides of Li, Na, K, Rb and Cs, and rare earth metal oxides such as oxides of Ce, La, Pr and Nd in combination with precious metal catalysts such as platinum dispersed on an alumina support have been used in the purification of exhaust gas from an internal combustion engine.
  • alkaline earth metal oxides such as oxides of Mg, Ca, Sr and Ba
  • alkali metal oxides such as oxides of Li, Na, K, Rb and Cs
  • rare earth metal oxides such as oxides of Ce, La, Pr and Nd in combination with precious metal catalysts such as platinum dispersed on an alumina support
  • precious metal catalysts such as platinum dispersed on an alumina support
  • baria is usually preferred because it forms nitrates at lean engine operation and releases the nitrates relatively easily under rich conditions.
  • NO x storage materials comprising barium fixed to ceria particles have been reported, and these NO x materials have exhibited improved thermal aging properties compared to the catalyst materials described above.
  • improvements there is an ongoing need to improve the performance of NO x storage materials, particularly the ability of these materials to operate over a wide temperature range and to operate effectively after exposure to high temperature. It is also desirable to improve the kinetics of NO x oxidation (required in advance of NOx storage) and the kinetics of NOx reduction (required following NOx release).
  • NO x storage materials comprising barium fixed to ceria particles have been reported, and these NO x materials have exhibited improved thermal aging properties compared to the catalyst materials described above.
  • aspects of the invention include nitrogen oxide storage materials, catalytic traps for the abatement of nitrogen oxide, methods for manufacturing both the nitrogen oxide storage materials and the catalytic traps for the abatement of nitrogen oxides, and methods of abating nitrogen oxide in an exhaust gas stream.
  • the nitrogen oxide storage materials comprise ceria particles having alkaline earth oxides, for example, baria, supported on the particles, the ceria having a crystallite size of between about 10 and 20 nm and the alkaline earth oxides having a crystallite size of between about 20 and 40 nm.
  • Other suitable alkaline earth oxides include oxides of Mg, Sr, and Ca.
  • the composite particles have a BET surface area of between about 30 and 80 m 2 /g.
  • a nitrogen oxide storage catalyst is provided comprising a coating on a substrate, the coating comprising a nitrogen oxide storage material comprising spray-dried ceria particles having baria supported on the particles.
  • the coating of the nitrogen oxide storage catalyst further comprises at least one member of platinum group metals selected from the group consisting of platinum, palladium, rhodium, iridium and mixtures thereof supported on refractory oxide particles.
  • the refractory oxide particles may be selected from the group consisting of aluminum oxide, mixed aluminum oxide and zirconium oxide, mixed aluminum oxide and lanthanum oxide, mixed aluminum oxide and cerium oxide, mixed aluminum oxide and magnesium oxide, and alumina oxide mixed with one or more of zirconia and lanthana.
  • the catalytic trap comprises a catalytic trap material including a precious metal catalytic component effective for oxidizing NO to NO 2 under lean conditions and promoting the reduction of released NO x to nitrogen under stoichiometric or rich conditions supported on a refractory metal oxide, and a NO x storage material effective for adsorbing the NO x under lean conditions and desorbing the NO x under stoichiometric or rich conditions, the NOx storage material comprising particles of ceria having alkaline earth carbonate supported on the ceria particles, having a crystallite size of between about 10 and 20 nm and the alkaline earth oxide having a crystallite size of between about 20 and 40 nm, and the catalytic trap material being disposed on a refractory carrier
  • Still another embodiment relates to a method of making a nitrogen oxide storage material comprising mixing a solution of barium with ceria particles, spray drying the particles, heating the spray-dried particles, mixing the composite particles with a precious metal supported catalyst and coating the slurry mixture of particles on a substrate.
  • FIG. 1 is a graph showing the nitrogen oxide conversion efficiency of a catalyst in accordance with an embodiment of the invention and a comparative reference catalyst;
  • FIG. 2 is a graph comparing the nitrogen oxide storage capacity of various catalysts
  • FIG. 3 is a graph comparing the nitrogen oxide storage capacity of catalysts
  • FIG. 4 is a graph comparing the nitrogen oxide storage capacity of two catalysts
  • FIG. 5 is a graph comparing the nitrogen oxide storage capacity of two catalysts.
  • FIG. 6 is a SEM image of the spray dried and calcined BaCO 3 /CeO 2 composite material.
  • a spray-dried NO x storage material comprising alkaline earth carbonate or mixtures of carbonates, for example, BaCO 3 or mixtures of BaCO 3 and MgCO 3 supported on CeO 2 particles is provided.
  • Ba sintering and Ba composite compound formation is reduced under the conditions of thermal stress in an exhaust gas of a lean burn engine.
  • the NO x storage material according to embodiments of the present invention demonstrates improved NO x storage capacity after thermal aging when used in a catalytic trap.
  • methods of manufacturing NO x storage materials and catalytic traps including these storage materials are provided.
  • Other embodiments of the invention pertain to a catalytic trap for abatement of NO x in an exhaust gas stream which is generated by an internal combustion engine which is operated periodically between lean and stoichiometric or rich conditions.
  • the catalytic trap comprises a catalytic trap material including a catalytic component effective for promoting the reduction of NO x under stoichiometric or rich conditions supported on a refractory metal oxide and a NO x storage material effective for adsorbing the NO x under lean conditions and desorbing and reducing the NO x to nitrogen under stoichiometric or rich conditions, the NOx storage material comprising spray-dried particles of ceria having alkaline earth carbonate, for example, barium carbonate, supported on the ceria particles, the catalytic trap material being disposed on a refractory carrier member.
  • Embodiments of this invention pertain to a process for abatement of NO x in an exhaust gas stream generated by an internal combustion engine which periodically operates alternately between lean and stoichiometric or rich conditions, comprising locating the above-described catalytic trap in an exhaust passage of the engine and treating the exhaust gas stream with a catalytic trap whereby at least some of the NO x in the exhaust gas stream is adsorbed by the catalytic trap during the periods of lean conditions and is desorbed from the catalytic trap and reduced to nitrogen during the periods of stoichiometric or rich conditions.
  • the refractory metal oxide support of the catalytic trap may be porous in nature and has a high surface area such as alumina, for example, gamma-alumina.
  • suitable support materials include titania, titania-alumina, zirconia, zirconia-alumina, baria-alumina, lanthana-alumina, lanthana-zirconia-alumina titania-zirconia, and mixtures thereof.
  • the refractory metal oxide support will have a surface area of between about 5 and about 350 m 2 /g, and more particularly between about 100 and 200 m 2 /g.
  • the support will be present on the coated substrate in the amount of about 1.5 to about 7.0 g/in 3 , for example between about 3 and 6 g/in 3 .
  • a suitable support material for the precious metal is alumina, which may be doped with one or more other materials.
  • the catalytic component preferably comprises a precious metal component, i.e., a platinum group metal component. Suitable precious metal components include platinum, palladium, rhodium and mixtures thereof.
  • the catalytic component will typically be present in an amount of about 20 to about 200 g/ft 3 , more specifically, about 60 to 120 g/ft 3 .
  • the NO x storage material employed in the catalytic trap according to embodiments of the present invention comprises a spray-dried NO x storage material comprising BaCO 3 supported on CeO 2 particles.
  • the catalytic trap is disposed on a refractory carrier member.
  • substrates include, for example, stainless steel, titanium, aluminum zirconate, aluminum titanate, aluminum phosphate, cordierite, mullite and corundum.
  • the carrier member may be employed as a monolithic honeycomb structure, spun fibers, corrugated foils, layered materials, etc.
  • a catalytic device employing a three-way conversion (“TWC”) catalyst may be used in conjunction with the catalytic trap of the invention.
  • TWC three-way conversion
  • the TWC catalyst would typically include platinum, palladium and rhodium catalytic components dispersed on a high surface area refractory support and may also contain one or more base metal oxide catalytic components such as oxides of iron, manganese or nickel.
  • Such catalysts can be stabilized against thermal degradation by expedients such as impregnating an activated alumina support with one or more rare earth metal oxides, e.g., ceria.
  • Such stabilized catalysts can sustain very high operating temperatures. For example, if a fuel cut technique is utilized, temperatures as high as 1050° C. may be sustained in the catalytic device.
  • the catalytic device would be mounted close to the exhaust manifold of the engine.
  • the TWC catalyst would warm up quickly and provide for efficient cold start emission control.
  • the TWC catalyst will remove HC, CO and NO x from the exhaust gas stream during stoichiometric or rich operation and HC and CO during lean operation.
  • the catalytic trap of the invention would be positioned downstream of the catalytic device where the exhaust gas temperature enables maximum NO x trap efficiency. During periods of lean engine operation, when NO x passes through the TWC catalyst, NO x is stored on the catalytic trap.
  • the catalytic trap is periodically desorbed and the NO x is reduced to nitrogen under periods of stoichiometric or rich engine operation.
  • a catalytic device containing a TWC catalyst may be employed downstream of the catalytic trap of the invention. Such catalytic device will serve to remove further amounts of HC and CO from the exhaust gas stream and, in particular, will provide for efficient reduction of the NO x to nitrogen under periods of stoichiometric or rich engine operation.
  • the catalytic NOx-trap may be used in conjunction with a diesel oxidation catalyst (DOC), and a catalyzed soot filter (CSF); where the DOC and CSF are placed either before or after the catalytic device of this invention.
  • DOC diesel oxidation catalyst
  • CSF catalyzed soot filter
  • the several components of the catalytic trap material may be applied to the refractory carrier member, i.e., the substrate, as a mixture of two or more components or as individual components in sequential steps in a manner which will be readily apparent to those skilled in the art of catalyst manufacture.
  • a typical method of manufacturing the catalytic trap of the present invention is to provide the catalytic trap material as a coating or layer of washcoat on the walls of the gas-flow passages of a suitable carrier member.
  • This may be accomplished, by impregnating a fine particulate refractory metal oxide support material, e.g., gamma alumina, with one or more catalytic metal components such as a precious metal, i.e., platinum group, compound or other noble metals or base metals, drying and calcining the impregnated support particles and forming an aqueous slurry of these particles.
  • a precious metal i.e., platinum group, compound or other noble metals or base metals
  • Spray-dried particles of the bulk NO x sorbent may be included in the slurry.
  • the NO x storage material or sorbent may be dispersed into the support, preferably in an impregnation operation, as described below.
  • Activated alumina may be thermally stabilized before the catalytic components are dispersed thereon, as is well known in the art, by impregnating it with, e.g., a solution of a soluble salt of barium, lanthanum, zirconium, rare earth metal or other suitable stabilizer precursor, and thereafter drying (e.g., at 110° C. for one hour) and calcining (e.g., at 550° C. for one hour) the impregnated activated alumina to form a stabilizing metal oxide dispersed onto the alumina.
  • a solution of a soluble salt of barium, lanthanum, zirconium, rare earth metal or other suitable stabilizer precursor e.g., a solution of a soluble salt of barium, lanthanum, zirconium, rare earth metal or other suitable stabilizer precursor, and thereafter drying (e.g., at 110° C. for one hour) and calcining (e.g., at 550° C.
  • Base metal catalysts may optionally also have been impregnated into the activated alumina, for example, by impregnating a solution of a base metal nitrate into the alumina particles and calcining to provide a base metal oxide dispersed in the alumina particles.
  • the carrier may then be immersed into the slurry of impregnated activated alumina and excess slurry removed to provide a thin coating of the slurry on the walls of the gas-flow passages of the carrier.
  • the coated carrier is then dried and calcined to provide an adherent coating of the catalytic component and, optionally, the catalytic trap material, to the walls of the passages thereof.
  • the carrier may then be immersed into a slurry of fine particles of component of the NO x storage material as a second or overlayer coating deposited over the layer of catalytic component.
  • a magnesium component e.g., a solution of a magnesium salt such as magnesium nitrate, acetate, sulfate, hydroxide, etc.
  • a magnesium component e.g., a solution of a magnesium salt such as magnesium nitrate, acetate, sulfate, hydroxide, etc.
  • the carrier is then dried and calcined to provide a finished catalyst trap member in accordance with one embodiment of the present invention.
  • the alumina or other support particles impregnated with the catalytic component may be mixed with bulk or supported particles of the NO x storage material in an aqueous slurry, and this mixed slurry of catalytic component particles and NO x storage material particles may be applied as a coating to the walls of the gas-flow passages of the carrier.
  • the washcoat of catalytic component material after being dried and calcined, is immersed (post-dipped) into a solution of a component (NO x storage material precursor compound (or complex) and a magnesium precursor compound (or complex) to impregnate the washcoat with the NO x storage material precursor.
  • the impregnated washcoat is then dried and calcined to provide the NO x storage material dispersed throughout the washcoat.
  • washcoat Separate discrete layers of washcoat may be applied in successive impregnating/drying/calcining operations, e.g., to provide a bottom washcoat layer containing a platinum catalytic component in a bottom washcoat layer and a palladium and/or rhodium catalytic component in a top washcoat layer.
  • the NO x storage material may be dispersed by impregnation into both the top and bottom layers.
  • the exhaust gas stream which is contacted with the catalytic trap of the present invention is alternately adjusted between lean and stoichiometric/rich operating conditions so as to provide alternating lean operating periods and stoichiometric/rich operating periods.
  • the exhaust gas stream being treated may be selectively rendered lean or stoichiometric/rich either by adjusting the air-to-fuel ratio fed to the engine generating the exhaust or by periodically injecting a reductant into the gas stream upstream of the catalytic trap.
  • the composition of the present invention is well suited to treat the exhaust of engines, including diesel engines, which continuously run lean.
  • a suitable reductant such as fuel
  • a suitable reductant such as fuel
  • Partial lean-burn engines such as partial lean-burn gasoline engines, are designed with controls which cause them to operate lean with brief, intermittent rich or stoichiometric conditions.
  • BaCO 3 and CeO 2 were intimately mixed and finely dispersed in a weight ratio of between about 1:3 and about 1:5.
  • Cerium oxide having a BET surface area of between about 50-150 m 2 /g was mixed with a solution of barium acetate such that the BaCO 3 /CeO 2 composite had a BaCO 3 content of about 10-30 wt %.
  • the suspension of soluble barium acetate and CeO 2 was then spray-dried at a temperature of between about 90° C. and 120° C. to obtain a solid mixture of barium acetate and ceria.
  • the mixture was then heated at about 550° C. to 800° C. for about 2 hours to form particles of ceria having barium carbonate supported on the ceria particles.
  • the resulting BaCO 3 had a crystallite size of between about 20 and 40 nm.
  • the BaCO 3 and CeO 2 crystallites formed particles with a size of between about 5 and 50 microns.
  • the BET surface area of the particulate mixture is between about 30 and 80 m 2 /g.
  • a precious metal can be supported on a refractory oxide according to the following description.
  • Pt and Rh are impregnated onto Al 2 O 3 by an incipient wetness procedure to yield 1.8 weight percent Pt and 0.1 weight percent Rh.
  • Pd is impregnated separately onto alumina to a Pd loading of 1.4 weight percent.
  • a slurry mixture containing about 34 wt % of alumina previously mixed with Pt/Rh, about 9 wt % Pd on alumina, a solution of zirconium acetate with a content of about 3 wt % ZrO 2 , magnesium acetate to yield 9 wt % MgO, and 45 wt % BaCO 3 /CeO 2 spray-dried powder is milled at pH 6-8 until a particle size of 11 micron (d 90 ) is obtained.
  • Ceramic or metallic honeycomb substrates are coated with the slurry in a dip coating manner and then dried in a dryer and subsequently calcined in a furnace under air at about 450° C.-550° C. The coating procedure is then repeated until a loading of about 4-6.5 g/in 3 is achieved.
  • the coating on the honeycomb catalyst comprises about 3-30 micron BaCO 3 /CeO 2 particles and about 1-20 micron alumina particles. BaCO 3 is fixed within the pores of the ceria particles in such a way that it does not migrate to the alumina particles. It is believed that the contact of BaCO 3 and alumina would lead to the formation of inactive Ba/Al 2 O 3 composite compound formation upon aging, which has a reduced NO x storage capacity compared to BaCO 3 .
  • catalytic traps Two catalytic traps were prepared, a first catalytic trap was prepared in accordance with Example 1 and a comparative catalytic trap was prepared in accordance with Comparative Example 2. Both catalytic traps A were evaluated after aging for 8 hours at 850° C.
  • Both catalytic traps were evaluated as follows. An engine was set to an air/fuel ratio of 11.6 for 2 minutes at the desired temperature to remove all stored NO x and oxygen from the catalyst. This mode represents rich engine operation. Subsequently, the engine was adjusted to an air/fuel ratio of 29.6 under constant NO x mass flow. This mode represents lean engine operation. During the whole test, the NO x concentration was measured before and after the NO x trap using a NO x analyzer.
  • FIG. 1 demonstrates that the NO x storage capacity of catalytic trap prepared in accordance with Example 1 utilizing a spray-drying process exhibited superior capacity compared to the Comparative reference Example.
  • Table I shows the result of a variation of the BaCO 3 and CeO 2 concentration together with a variation of the ceria used. After impregnation, all samples were calcined at 550° C. in air to decompose the impregnated Ba precursor into BaCO 3 .
  • sample C After 800° C. aging, the highest NOx storage activity at 400° C. is obtained with sample C, having a medium Ba concentration and a CeO 2 material with a medium BET surface area and crystallinity.
  • a high BET surface area and relative low Ba concentration is especially beneficial for NOx storage at 300° C. It is particularly interesting that sample D having the largest BaCO 3 crystallite size after aging yields the best NOx storage at low temperature.
  • increased Ba concentration resulted in decreased BET surface area and increase in CeO 2 crystal size.
  • the Ba/CeO 2 is calcined after Ba impregnation at different temperatures. This is done to decompose the Ba precursor to the carbonate and to conditioning the composite for optimum NOx adsorption capacity.
  • Table II demonstrates that a calcination temperature between 550 and 750° C. after impregnation of Ba onto CeO 2 provided the best results for NO x storage. The samples calcined within this temperature range had higher surface area and exhibited higher NOx storage after aging than a sample calcined at 850° C.
  • a BaCO 3 crystallite size of between about 20-50 nm, for example, 45 nm, and a CeO 2 crystallite size of between about 25-30 nm in combination with a sufficient BET surface area after aging yielded the highest NOx storage at 400° C.
  • an as-prepared BET surface area between 40-60 m 2 /g and a ceria crystal size between about 10-and 20 nm and a BaCO 3 crystallite size of between about 20-and 40 nm yielded the best performance after aging.
  • FIG. 6 shows about 10-20 nm size CeO 2 crystals agglomerated to particles of about 5-50 microns in size. Adhering to these about 5-50 micron size CeO 2 particles are BaCO 3 particles of about 20-150 nm size. The BaCO 3 particles are likely agglomerates of smaller crystallites.
  • the decomposition temperature is the temperature at which Ba reacts with ceria to form BaCeO 3 .
  • the samples below were prepared by an incipient wetness preparation instead of spray-drying prior to calcination. The results are shown in Table III:
  • the preferred BaCO 3 /CeO 2 /dopand material should have a BET surface area >10 m 2 /g after aging and a high resistance towards reaction to BaCO 3 as shown in table III.
  • the table below shows a list of different support materials derived from ZrO 2 or Al 2 O 3 .
  • Materials A and B show higher BaCO 3 decomposition temperature than pure or La, Ba or ZrO 2 doped aluminas. However the surface area of those materials is relatively small compared to other doped or undoped materials. Furthermore, it was found that the higher the surface area of a material in presence of Ba the higher is the NO x storage capacity of an aged catalyst containing this material.
  • ZrO 2 doped aluminas and also La and ZrO 2 doped materials have very thermally stable surface areas in presence of Ba.
  • the preferred alumina should have a BET surface area of 150-250 m 2 /g, a pore volume of 0.3-0.8 ml/g an average pore size of 3-20 nm.
  • Samples N (Example 8A) and O (Example 8B) from Table IV above were prepared into fully formulated catalysts and tested for NOx storage capacity after aging for 50 hours at 850° C. under stoichiometric conditions.
  • FIG. 4 shows that the lanthana and zirconia doped sample (Example O) exhibited the best results between 250 and 400° C. Similar results were observed for sample N aged 50 hours at 750° C. (Example 8C) and sample O aged 50 hours at 750° C. (Example 8D) at a lean air fuel ratio, and these results are shown in FIG. 5 .

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US11/564,494 US20080120970A1 (en) 2006-11-29 2006-11-29 NOx Storage Materials and Traps Resistant to Thermal Aging
RU2009124599/04A RU2009124599A (ru) 2006-11-29 2007-11-28 Материалы для накопления nox и ловушки, устойчивые к термическому старению
CN200780050588XA CN101610844B (zh) 2006-11-29 2007-11-28 抗热老化的NOx储存材料和捕集器
EP17179750.9A EP3257582A1 (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
ES07854809.6T ES2458499T5 (es) 2006-11-29 2007-11-28 Método para preparación de un material de almacenamiento de NOx
ES13172000.5T ES2650736T3 (es) 2006-11-29 2007-11-28 Catalizador de almacenamiento de NOx y proceso para la extinción de NOx
DE202007019526U DE202007019526U1 (de) 2006-11-29 2007-11-28 NOx-Speichermaterialien und -Fallen, die gegenüber Wärmealterung beständig sind
DE202007019493U DE202007019493U1 (de) 2006-11-29 2007-11-28 NOx-Speichermaterialien und -Fallen, die gegenüber Wärmealterung beständig sind
CA2671020A CA2671020C (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
EP13172000.5A EP2644271B1 (en) 2006-11-29 2007-11-28 Nox storage catalyst and process for the abatement of nox
EP07854809.6A EP2104567B2 (en) 2006-11-29 2007-11-28 Method of making a NOx storage material
BRPI0719512A BRPI0719512B1 (pt) 2006-11-29 2007-11-28 catalisador de armazenamento de óxido de nitrogênio, captador catalítico, e, método para fabricar um material de armazenamento de óxido de nitrogênio.
KR1020097013366A KR101391005B1 (ko) 2006-11-29 2007-11-28 열노화에 대해 내성을 갖는 ｎｏｘ 저장 물질 및 트랩
PCT/US2007/085759 WO2008067375A1 (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
MX2009005675A MX2009005675A (es) 2006-11-29 2007-11-28 Materiales de almacenamiento de nox y trampas resistentes al envejecimiento termico.
JP2009539458A JP2010510884A (ja) 2006-11-29 2007-11-28 熱時効耐性ＮＯｘ貯蔵材料及びトラップ
ARP070105314A AR064038A1 (es) 2006-11-29 2007-11-29 Materiales y trampas para almacenamiento de nox resistentes al envejecimiento termico
ZA200904435A ZA200904435B (en) 2006-11-29 2009-06-25 Nox storage materials and traps resistant to thermal aging
US12/497,846 US8022010B2 (en) 2006-11-29 2009-07-06 NOx storage materials and traps resistant to thermal aging
US13/272,007 US8592337B2 (en) 2006-11-29 2011-10-12 NOx storage materials and traps resistant to thermal aging

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080167181A1 (en) * 2007-01-10 2008-07-10 Nissan Motor Co., Ltd. Exhaust gas purifying catalyst and producing method thereof
US20100111789A1 (en) * 2006-08-31 2010-05-06 Franck Fajardie Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate
CN101811039A (zh) * 2010-03-12 2010-08-25 浙江大学 一种硫改性二氧化铈催化剂的制备方法及制备的催化剂
US20100263357A1 (en) * 2006-06-29 2010-10-21 Dieter Lindner Three way catalyst
US20100275579A1 (en) * 2007-09-28 2010-11-04 Umicore Ag & Co Kg Removal of particulates from the exhaust gas of internal combustion engines operated with a predominantly stoichiometric air/fuel mixture
US20100290964A1 (en) * 2009-05-18 2010-11-18 Southward Barry W L HIGH Pd CONTENT DIESEL OXIDATION CATALYSTS WITH IMPROVED HYDROTHERMAL DURABILITY
US20110099975A1 (en) * 2009-11-03 2011-05-05 Owen Herman Bailey Architectural diesel oxidation catalyst for enhanced no2 generator
US20110120093A1 (en) * 2008-04-24 2011-05-26 Stephan Eckhoff Process and apparatus for purifying exhaust gases from an internal combustion engine
US20110126527A1 (en) * 2008-07-31 2011-06-02 Basf Se Nox storage materials and traps resistant to thermal aging
US8853123B2 (en) * 2012-12-18 2014-10-07 Hyundai Motor Company LNT catalyst with enhanced nitrogen oxide storage capacity at low temperature
US20150336085A1 (en) * 2013-01-08 2015-11-26 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
WO2016033046A1 (en) * 2014-08-25 2016-03-03 Basf Corporation Catalyst with improved hydrothermal stability
US20160082427A1 (en) * 2013-04-26 2016-03-24 Umicore Ag & Co. Kg Desulfurization of nox storage catalysts
US20170314438A1 (en) * 2016-04-29 2017-11-02 Johnson Matthey Public Limited Company Exhaust System
US20170362984A1 (en) * 2014-12-08 2017-12-21 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
US20180311648A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company NOx ADSORBER CATALYST
US20180311649A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company NOx ADSORBER CATALYST
US20180311647A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company THREE LAYER NOx ADSORBER CATALYST
CN109310993A (zh) * 2016-05-05 2019-02-05 庄信万丰股份有限公司 NOx吸附剂催化剂
US10213768B2 (en) * 2016-09-02 2019-02-26 Johnson Matthey Public Limited Company NOx trap
US10449522B2 (en) * 2015-07-30 2019-10-22 Basf Corporation Process for manufacture of NOx storage materials
US10801382B2 (en) * 2017-04-28 2020-10-13 Cataler Corporation Exhaust gas-purifying catalyst
US10807071B2 (en) * 2016-05-05 2020-10-20 University Of Connecticut Mesoporous metal doped cerium oxide catalyst
CN113318736A (zh) * 2020-02-28 2021-08-31 株式会社斯巴鲁 汽油贫燃发动机用lnt层叠催化剂、及使用其的废气净化装置
US11344875B2 (en) * 2017-08-28 2022-05-31 Heesung Catalysts Corporation NOx-trapping catalyst having non-platinum-group-metal NOx-trapping layer
EP4023600A4 (en) * 2021-08-12 2022-12-21 Daiichi Kigenso Kagaku Kogyo Co., Ltd. ZIRCONIA-BASED POROUS BODIES AND METHOD FOR PRODUCING ZIRCONIA-BASED POROUS BODIES

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080120970A1 (en) 2006-11-29 2008-05-29 Marcus Hilgendorff NOx Storage Materials and Traps Resistant to Thermal Aging
US8507403B2 (en) 2008-06-27 2013-08-13 Cabot Corporation Process for producing exhaust treatment catalyst powders, and their use
US8920759B2 (en) * 2009-03-02 2014-12-30 GM Global Technology Operations LLC Method and apparatus for reducing NOx emissions from a lean burning hydrocarbon fueled power source
JP5565569B2 (ja) * 2009-04-07 2014-08-06 株式会社豊田中央研究所 排ガス浄化用触媒
US8758695B2 (en) 2009-08-05 2014-06-24 Basf Se Treatment system for gasoline engine exhaust gas
US8784759B2 (en) 2010-06-10 2014-07-22 Basf Se NOx storage catalyst with reduced Rh loading
JP5876475B2 (ja) 2010-06-10 2016-03-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Ｒｈ負荷が低減されたＮＯｘ貯蔵触媒
GB201021649D0 (en) 2010-12-21 2011-02-02 Johnson Matthey Plc NOx Absorber catalyst
DE102011078326A1 (de) * 2011-06-29 2013-01-03 Ford Global Technologies, Llc LNT zur NOx-Entfernung aus Abgasen von Verbrennungskraftmaschinen
JP5641360B2 (ja) * 2011-12-08 2014-12-17 トヨタ自動車株式会社 排ガス浄化用触媒及びその利用
JP5992192B2 (ja) * 2012-03-30 2016-09-14 三井金属鉱業株式会社 パラジウム触媒
US9611774B2 (en) 2013-03-13 2017-04-04 Basf Corporation Catalyst with improved hydrothermal stability
US9034287B2 (en) * 2013-03-13 2015-05-19 Basf Corporation Catalyst compositions, articles, methods and systems
RU2015143276A (ru) 2013-03-13 2017-04-19 Басф Корпорейшн КАТАЛИЗАТОР-НАКОПИТЕЛЬ NOх С УЛУЧШЕННЫМИ ГИДРОТЕРМАЛЬНОЙ УСТОЙЧИВОСТЬЮ И СТЕПЕНЬЮ ПРЕВРАЩЕНИЯ NOх
DE102013210270A1 (de) 2013-06-03 2014-12-04 Umicore Ag & Co. Kg Dreiwegkatalysator
CN105358249B (zh) * 2013-07-08 2018-04-10 优美科触媒日本有限公司 氮氧化物去除用催化剂
US9744529B2 (en) * 2014-03-21 2017-08-29 Basf Corporation Integrated LNT-TWC catalyst
WO2015143225A1 (en) * 2014-03-21 2015-09-24 SDCmaterials, Inc. Compositions for passive nox adsorption (pna) systems
US9527033B2 (en) 2015-01-23 2016-12-27 Toyota Motor Engineering & Manufacturing North America, Inc. Mixed metal oxide catalyst
BR112017018826A2 (pt) * 2015-03-03 2018-04-24 Basf Corp artigo de tratamento de escape, sistema de tratamento de gases e método de monitoramento do envelhecimento de um catalisador
GB201518996D0 (en) * 2015-10-27 2015-12-09 Magnesium Elektron Ltd Zirconia-based compositions for use as three-way catalysts
KR102429131B1 (ko) * 2016-06-10 2022-08-05 존슨 맛쎄이 퍼블릭 리미티드 컴파니 NOx 흡착제 촉매
US20190143311A1 (en) * 2016-06-23 2019-05-16 N.E. Chemcat Corporation Catalyst for lean burn
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US10920645B2 (en) 2018-08-02 2021-02-16 Ford Global Technologies, Llc Systems and methods for on-board monitoring of a passive NOx adsorption catalyst
CN109603823B (zh) * 2019-01-09 2022-08-02 无锡威孚环保催化剂有限公司 柴油机尾气净化系统的稀燃NOx捕集催化剂及其制备方法
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CN113351152A (zh) * 2021-04-24 2021-09-07 化学与精细化工广东省实验室 一种氮氧化物吸收复合材料
CN116237036B (zh) * 2023-01-31 2024-08-23 昆明贵研催化剂有限责任公司 一种氮氧化物储存材料、制备方法及其应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359133A (en) * 1964-04-06 1967-12-19 American Lava Corp Ceramic dielectrics
US5064803A (en) * 1990-08-31 1991-11-12 Allied-Signal Inc. Preparation of three-way catalysts with highly dispersed ceria
US5075275A (en) * 1989-07-06 1991-12-24 Mazda Motor Corporation Catalyst for purification of exhaust gases
US5874057A (en) * 1995-07-12 1999-02-23 Engelhard Corporation Lean NOx catalyst/trap method
US5965481A (en) * 1993-05-14 1999-10-12 Institut Francais Du Petrole Process for preparing a catalyst suitable for the treatment of exhaust gases from internal combustion engines
US6090191A (en) * 1999-02-23 2000-07-18 Oktrytoe Aktsionernoe Obschestvo "Nauchno-Proizvodstvennoe Obiedinenie "Energomash" Imeni Akademika V.P. Glushko" Compound for producing a metal-ceramic coating
US6180558B1 (en) * 1996-03-29 2001-01-30 Mazda Motor Corporation Material for exhaust gas purifying catalyst, exhaust gas purifying catalyst made of the material and method for producing the exhaust gas purifying catalyst
US6350421B1 (en) * 1998-08-24 2002-02-26 Dmc2 Degussa Metals Catalysts Cerdec Ag Nitrogen oxide storage material and nitrogen oxide storing catalyst prepared therefrom
US6602820B1 (en) * 1999-11-17 2003-08-05 Degussa-Huls Aktiengesellschaft Method for producing a nitrogen oxide storage material and a storage material made with it
US6858193B2 (en) * 2001-11-30 2005-02-22 Umicore Ag & Co. Kg Catalyst for lowering the amount of nitrogen oxides in the exhaust gas from lean burn engines
US7166263B2 (en) * 2002-03-28 2007-01-23 Utc Fuel Cells, Llc Ceria-based mixed-metal oxide structure, including method of making and use

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3222219A (en) * 1961-11-29 1965-12-07 Phelps Dodge Copper Prod Ceramic-coated electrically-conductive wire and method of making same
GB1077735A (en) * 1964-08-14 1967-08-02 Power Jets Res & Dev Ltd Coatings for metallic materials
US3518206A (en) * 1968-05-17 1970-06-30 Du Pont Supported catalysts composed of substrate coated with colloidal silica and catalyst
NL7400525A (es) * 1973-01-27 1974-07-30
JPS5428787A (en) 1977-08-08 1979-03-03 Hitachi Ltd Process for producing gaseous waste purifying catalyst
US4374173A (en) * 1979-11-06 1983-02-15 Sherritt Gordon Mines Limited Composite powders sprayable to form abradable seal coatings
US4277374A (en) * 1980-01-28 1981-07-07 Allegheny Ludlum Steel Corporation Ferritic stainless steel substrate for catalytic system
JPS57117347A (en) 1981-01-12 1982-07-21 Toshiba Corp Method for coating catalyst film
FR2530489B1 (fr) * 1982-07-26 1987-02-27 Pro Catalyse Procede de fabrication de catalyseurs pour le traitement des gaz d'echappement des moteurs a combustion interne
US4904518A (en) * 1988-06-29 1990-02-27 Uop Multiphase composite and processes for preparing same
US5244852A (en) * 1988-11-18 1993-09-14 Corning Incorporated Molecular sieve-palladium-platinum catalyst on a substrate
CN1018984B (zh) * 1989-05-17 1992-11-11 中国科学技术大学 含铜、镧氧化物的废气净化催化剂及其制法
US5168085A (en) * 1991-05-20 1992-12-01 Corning Incorporated Multi-stage twc system
US5204302A (en) * 1991-09-05 1993-04-20 Technalum Research, Inc. Catalyst composition and a method for its preparation
GB9203394D0 (en) * 1992-02-18 1992-04-01 Johnson Matthey Plc Coated article
FR2701472B1 (fr) 1993-02-10 1995-05-24 Rhone Poulenc Chimie Procédé de préparation de compositions à base d'oxydes mixtes de zirconium et de cérium.
JP3550709B2 (ja) * 1993-05-28 2004-08-04 マツダ株式会社 排気ガス浄化用触媒の製造方法
JP3447384B2 (ja) * 1993-09-29 2003-09-16 本田技研工業株式会社 排気ガス浄化用触媒
US5422331A (en) * 1994-02-25 1995-06-06 Engelhard Corporation Layered catalyst composition
US6214303B1 (en) * 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
EP0745416B1 (en) * 1995-06-02 2003-09-17 Corning Incorporated Device for removal of contaminants from fluid streams
JP4201356B2 (ja) 1996-06-20 2008-12-24 本田技研工業株式会社 内燃機関用排ガス浄化装置
FR2771306B1 (fr) * 1997-11-25 2000-02-04 Rhodia Chimie Sa Composition a base de manganese et utilisation comme piege a nox pour le traitement de gaz d'echappement
US20010027165A1 (en) * 1998-05-01 2001-10-04 Michael P. Galligan Catalyst members having electric arc sprayed substrates and methods of making the same
DE19838282A1 (de) * 1998-08-24 2000-03-02 Degussa Stickoxid-Speichermaterial und daraus hergestellter Stickoxid-Speicherkatalysator
US6559094B1 (en) * 1999-09-09 2003-05-06 Engelhard Corporation Method for preparation of catalytic material for selective oxidation and catalyst members thereof
CA2402999C (en) * 2001-01-11 2007-11-06 Ict Co., Ltd. Iridium catalyst for purifying nitrogen oxides in exhaust systems
US6725656B2 (en) * 2001-12-07 2004-04-27 Dan T. Moore Company Insulated exhaust manifold
WO2003050397A2 (en) 2001-12-07 2003-06-19 Dan T. Moore Company Insulated exhaust manifold having internal catalyst support body
WO2004035511A2 (en) 2002-10-16 2004-04-29 Conocophillips Company Fischer-tropsch processes and catalysts using stabilized supports
WO2005069767A2 (en) 2003-11-26 2005-08-04 Cabot Corporation Particulate absorbent materials and methods for making same
JP2006016237A (ja) 2004-06-30 2006-01-19 Sumitomo Osaka Cement Co Ltd 多孔質酸化物粒子の製造方法
DE102005034344A1 (de) * 2005-07-22 2007-01-25 Umicore Ag & Co. Kg Verfahren zur Reaktivierung thermisch gealterter Stickoxid-Speicherkatalysatoren
FR2901155B1 (fr) 2006-05-16 2008-10-10 Rhodia Recherches & Tech Compositions utilisees notamment pour le piegeage d'oxydes d'azote (nox)
JP4698505B2 (ja) * 2006-06-27 2011-06-08 戸田工業株式会社 排気ガス浄化用触媒
US20080120970A1 (en) 2006-11-29 2008-05-29 Marcus Hilgendorff NOx Storage Materials and Traps Resistant to Thermal Aging

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359133A (en) * 1964-04-06 1967-12-19 American Lava Corp Ceramic dielectrics
US5075275A (en) * 1989-07-06 1991-12-24 Mazda Motor Corporation Catalyst for purification of exhaust gases
US5064803A (en) * 1990-08-31 1991-11-12 Allied-Signal Inc. Preparation of three-way catalysts with highly dispersed ceria
US5965481A (en) * 1993-05-14 1999-10-12 Institut Francais Du Petrole Process for preparing a catalyst suitable for the treatment of exhaust gases from internal combustion engines
US5874057A (en) * 1995-07-12 1999-02-23 Engelhard Corporation Lean NOx catalyst/trap method
US6180558B1 (en) * 1996-03-29 2001-01-30 Mazda Motor Corporation Material for exhaust gas purifying catalyst, exhaust gas purifying catalyst made of the material and method for producing the exhaust gas purifying catalyst
US6350421B1 (en) * 1998-08-24 2002-02-26 Dmc2 Degussa Metals Catalysts Cerdec Ag Nitrogen oxide storage material and nitrogen oxide storing catalyst prepared therefrom
US6090191A (en) * 1999-02-23 2000-07-18 Oktrytoe Aktsionernoe Obschestvo "Nauchno-Proizvodstvennoe Obiedinenie "Energomash" Imeni Akademika V.P. Glushko" Compound for producing a metal-ceramic coating
US6602820B1 (en) * 1999-11-17 2003-08-05 Degussa-Huls Aktiengesellschaft Method for producing a nitrogen oxide storage material and a storage material made with it
US6858193B2 (en) * 2001-11-30 2005-02-22 Umicore Ag & Co. Kg Catalyst for lowering the amount of nitrogen oxides in the exhaust gas from lean burn engines
US7166263B2 (en) * 2002-03-28 2007-01-23 Utc Fuel Cells, Llc Ceria-based mixed-metal oxide structure, including method of making and use

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8663588B2 (en) * 2006-06-29 2014-03-04 Umicore Ag & Co. Kg Three way catalyst
US20100263357A1 (en) * 2006-06-29 2010-10-21 Dieter Lindner Three way catalyst
US20100111789A1 (en) * 2006-08-31 2010-05-06 Franck Fajardie Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate
US20080167181A1 (en) * 2007-01-10 2008-07-10 Nissan Motor Co., Ltd. Exhaust gas purifying catalyst and producing method thereof
US8877675B2 (en) * 2007-01-10 2014-11-04 Nissan Motor Co., Ltd. Exhaust gas purifying catalyst and producing method thereof
US20100275579A1 (en) * 2007-09-28 2010-11-04 Umicore Ag & Co Kg Removal of particulates from the exhaust gas of internal combustion engines operated with a predominantly stoichiometric air/fuel mixture
US8640440B2 (en) * 2007-09-28 2014-02-04 Umicore Ag & Co. Kg Removal of particulates from the exhaust gas of internal combustion engines operated with a predominantly stoichiometric air/fuel mixture
US20110120093A1 (en) * 2008-04-24 2011-05-26 Stephan Eckhoff Process and apparatus for purifying exhaust gases from an internal combustion engine
US20110126527A1 (en) * 2008-07-31 2011-06-02 Basf Se Nox storage materials and traps resistant to thermal aging
US9540980B2 (en) 2008-07-31 2017-01-10 Basf Se NOx storage materials and traps resistant to thermal aging
US20100290964A1 (en) * 2009-05-18 2010-11-18 Southward Barry W L HIGH Pd CONTENT DIESEL OXIDATION CATALYSTS WITH IMPROVED HYDROTHERMAL DURABILITY
US8246923B2 (en) * 2009-05-18 2012-08-21 Umicore Ag & Co. Kg High Pd content diesel oxidation catalysts with improved hydrothermal durability
US8557203B2 (en) 2009-11-03 2013-10-15 Umicore Ag & Co. Kg Architectural diesel oxidation catalyst for enhanced NO2 generator
US20110099975A1 (en) * 2009-11-03 2011-05-05 Owen Herman Bailey Architectural diesel oxidation catalyst for enhanced no2 generator
CN101811039A (zh) * 2010-03-12 2010-08-25 浙江大学 一种硫改性二氧化铈催化剂的制备方法及制备的催化剂
US8853123B2 (en) * 2012-12-18 2014-10-07 Hyundai Motor Company LNT catalyst with enhanced nitrogen oxide storage capacity at low temperature
US9662638B2 (en) * 2013-01-08 2017-05-30 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
US20150336085A1 (en) * 2013-01-08 2015-11-26 Umicore Ag & Co. Kg Catalyst for reducing nitrogen oxides
US20160082427A1 (en) * 2013-04-26 2016-03-24 Umicore Ag & Co. Kg Desulfurization of nox storage catalysts
CN106794447A (zh) * 2014-08-25 2017-05-31 巴斯夫公司 具有改进的水热稳定性的催化剂
WO2016033046A1 (en) * 2014-08-25 2016-03-03 Basf Corporation Catalyst with improved hydrothermal stability
US10634030B2 (en) * 2014-12-08 2020-04-28 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
US20170362984A1 (en) * 2014-12-08 2017-12-21 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
US11713705B2 (en) 2014-12-08 2023-08-01 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
US11149610B2 (en) 2014-12-08 2021-10-19 Basf Corporation Nitrous oxide removal catalysts for exhaust systems
US10449522B2 (en) * 2015-07-30 2019-10-22 Basf Corporation Process for manufacture of NOx storage materials
US20170314438A1 (en) * 2016-04-29 2017-11-02 Johnson Matthey Public Limited Company Exhaust System
US11358127B2 (en) 2016-05-05 2022-06-14 Johnson Matthey Public Limited Company NOx adsorber catalyst
CN109310993A (zh) * 2016-05-05 2019-02-05 庄信万丰股份有限公司 NOx吸附剂催化剂
US10807071B2 (en) * 2016-05-05 2020-10-20 University Of Connecticut Mesoporous metal doped cerium oxide catalyst
US10213768B2 (en) * 2016-09-02 2019-02-26 Johnson Matthey Public Limited Company NOx trap
US10603655B2 (en) * 2017-03-29 2020-03-31 Johnson Matthey Public Limited Company NOx adsorber catalyst
US10596550B2 (en) * 2017-03-29 2020-03-24 Johnson Matthey Public Limited Company Three layer NOx adsorber catalyst
US10974228B2 (en) * 2017-03-29 2021-04-13 Johnson Matthey Public Limited Company NOx adsorber catalyst
US20180311647A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company THREE LAYER NOx ADSORBER CATALYST
US20180311649A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company NOx ADSORBER CATALYST
US20180311648A1 (en) * 2017-03-29 2018-11-01 Johnson Matthey Public Limited Company NOx ADSORBER CATALYST
US10801382B2 (en) * 2017-04-28 2020-10-13 Cataler Corporation Exhaust gas-purifying catalyst
US11344875B2 (en) * 2017-08-28 2022-05-31 Heesung Catalysts Corporation NOx-trapping catalyst having non-platinum-group-metal NOx-trapping layer
CN113318736A (zh) * 2020-02-28 2021-08-31 株式会社斯巴鲁 汽油贫燃发动机用lnt层叠催化剂、及使用其的废气净化装置
US11686231B2 (en) 2020-02-28 2023-06-27 N.E. Chemcat Corporation LNT layered catalyst for lean burn gasoline engine and exhaust gas purification apparatus using the same
EP4023600A4 (en) * 2021-08-12 2022-12-21 Daiichi Kigenso Kagaku Kogyo Co., Ltd. ZIRCONIA-BASED POROUS BODIES AND METHOD FOR PRODUCING ZIRCONIA-BASED POROUS BODIES
US11958039B2 (en) 2021-08-12 2024-04-16 Daiichi Kigenso Kagaku Kogyo Co., Ltd. Zirconia-based porous body and method for manufacturing zirconia-based porous body

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