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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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English (en)
Inventor
Marcus Hilgendorff
Stanley Roth
Susanne Stiebels
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BASF Catalysts LLC
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BASF Catalysts LLC
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Application filed by BASF Catalysts LLC filed Critical BASF Catalysts LLC
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 EP17179750.9A priority patent/EP3257582A1/en
Priority to BRPI0719512A priority patent/BRPI0719512B1/pt
Priority to ES13172000.5T priority patent/ES2650736T3/es
Priority to EP13172000.5A priority patent/EP2644271B1/en
Priority to PCT/US2007/085759 priority patent/WO2008067375A1/en
Priority to DE202007019526U priority patent/DE202007019526U1/de
Priority to ES07854809.6T priority patent/ES2458499T5/es
Priority to EP07854809.6A priority patent/EP2104567B2/en
Priority to JP2009539458A priority patent/JP2010510884A/ja
Priority to CA2671020A priority patent/CA2671020C/en
Priority to CN200780050588XA priority patent/CN101610844B/zh
Priority to RU2009124599/04A priority patent/RU2009124599A/ru
Priority to KR1020097013366A priority patent/KR101391005B1/ko
Priority to DE202007019493U priority patent/DE202007019493U1/de
Priority to MX2009005675A priority patent/MX2009005675A/es
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
    • 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
    • B01J23/10—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
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    • 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
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    • 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
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    • 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
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    • B01D2255/1021—Platinum
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    • B01D2255/204—Alkaline earth metals
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    • B01D—SEPARATION
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    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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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
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
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    • 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
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • 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
DE202007019493U DE202007019493U1 (de) 2006-11-29 2007-11-28 NOx-Speichermaterialien und -Fallen, die gegenüber Wärmealterung beständig sind
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
RU2009124599/04A RU2009124599A (ru) 2006-11-29 2007-11-28 Материалы для накопления nox и ловушки, устойчивые к термическому старению
ES13172000.5T ES2650736T3 (es) 2006-11-29 2007-11-28 Catalizador de almacenamiento de NOx y proceso para la extinción de NOx
EP13172000.5A EP2644271B1 (en) 2006-11-29 2007-11-28 Nox storage catalyst and process for the abatement of nox
PCT/US2007/085759 WO2008067375A1 (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
DE202007019526U DE202007019526U1 (de) 2006-11-29 2007-11-28 NOx-Speichermaterialien und -Fallen, die gegenüber Wärmealterung beständig sind
ES07854809.6T ES2458499T5 (es) 2006-11-29 2007-11-28 Método para preparación de un material de almacenamiento de NOx
EP07854809.6A EP2104567B2 (en) 2006-11-29 2007-11-28 Method of making a NOx storage material
EP17179750.9A EP3257582A1 (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
CA2671020A CA2671020C (en) 2006-11-29 2007-11-28 Nox storage materials and traps resistant to thermal aging
CN200780050588XA CN101610844B (zh) 2006-11-29 2007-11-28 抗热老化的NOx储存材料和捕集器
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
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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