WO2008088649A1 - Engine exhaust catalysts containing palladium-gold - Google Patents

Engine exhaust catalysts containing palladium-gold Download PDF

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Publication number
WO2008088649A1
WO2008088649A1 PCT/US2007/088085 US2007088085W WO2008088649A1 WO 2008088649 A1 WO2008088649 A1 WO 2008088649A1 US 2007088085 W US2007088085 W US 2007088085W WO 2008088649 A1 WO2008088649 A1 WO 2008088649A1
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Prior art keywords
catalyst
emission control
washcoat
coated
supported
Prior art date
Application number
PCT/US2007/088085
Other languages
French (fr)
Inventor
Kyle L. Fujdala
Timothy J. Truex
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Nanostellar, Inc.
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Publication date
Priority to US11/624,116 priority Critical patent/US20080125313A1/en
Priority to US11/624,128 priority
Priority to US11/624,116 priority
Priority to US11/624,128 priority patent/US7709414B2/en
Priority to US11/942,710 priority
Priority to US11/942,710 priority patent/US7534738B2/en
Application filed by Nanostellar, Inc. filed Critical Nanostellar, Inc.
Priority claimed from CN2007800501179A external-priority patent/CN101583423B/en
Publication of WO2008088649A1 publication Critical patent/WO2008088649A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/52Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts 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
    • B01J23/56Platinum group metals
    • B01J23/63Platinum group metals with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts 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
    • B01J23/66Silver or gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843Arsenic, antimony or bismuth
    • B01J23/8437Bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/0006Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0244Coatings comprising several layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0246Coatings comprising a zeolite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0248Coatings comprising impregnated particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1021Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1023Palladium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/106Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/206Rare earth metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/40Mixed oxides
    • B01D2255/407Zr-Ce mixed oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/50Zeolites
    • B01D2255/502Beta zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/50Zeolites
    • B01D2255/504ZSM 5 zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/902Multilayered catalyst
    • B01D2255/9025Three layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/92Dimensions
    • B01D2255/9207Specific surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/01Engine exhaust gases
    • B01D2258/012Diesel engines and lean burn gasoline engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007Zeolite Beta
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites

Abstract

An emission control catalyst that exhibits improved CO and HC reduction performance includes a supported platinum-based catalyst, and a supported palladium-gold catalyst. The two catalysts are coated onto different layers, zones, or monoliths of the substrate for the emission control catalyst such that the platinum-based catalyst encounters the exhaust stream before the palladium-gold catalyst. Zeolite may be added to the emission control catalyst as a hydrocarbon absorbing component to boost the oxidation activity of the palladium-gold catalyst.

Description

ENGINE EXHAUST CATALYSTS CONTAINING PALLADIUM-GOLD

BACKGROUND OF THE INVENTION Field of the Invention

[0001] Embodiments of the present invention generally relate to supported catalysts containing precious group metals and, and more particularly, to engine exhaust catalysts containing palladium and gold, and methods of production thereof.

Description of the Related Art

[0002] Many industrial products such as fuels, lubricants, polymers, fibers, drugs, and other chemicals would not be manufacturable without the use of catalysts. Catalysts are also essential for the reduction of pollutants, particularly air pollutants created during the production of energy and by automobiles. Many industrial catalysts are composed of a high surface area support material upon which chemically active metal nanoparticles (i.e., nanometer sized metal particles) are dispersed. The support materials are generally inert, ceramic type materials having surface areas on the order of hundreds of square meters/gram. This high specific surface area usually requires a complex internal pore system. The metal nanoparticles are deposited on the support and dispersed throughout this internal pore system, and are generally between 1 and 100 nanometers in size.

[0003] Processes for making supported catalysts go back many years. One such process for making platinum catalysts, for example, involves the contacting of a support material such as alumina with a metal salt solution such as hexachloroplatinic acid in water. The metal salt solution "impregnates" or fills the pores of the support during this process. Following the impregnation, the support containing the metal salt solution would be dried, causing the metal salt to precipitate within the pores. The support containing the precipitated metal salt would then be calcined (typically in air) and, if necessary, exposed to a reducing gas environment (e.g., hydrogen or carbon monoxide) for further reduction to form metal particles. Another process for making supported catalysts involves the steps of contacting a support material with a metal salt solution and reducing the metal ions to metal particles in situ using suitable reducing agents. [0004] Supported catalysts are quite useful in removing pollutants from vehicle exhausts. Vehicle exhausts contain harmful pollutants, such as carbon monoxide (CO), unburned hydrocarbons (HC), and nitrogen oxides (NOx), that contribute to the "smog-effect" that have plagued major metropolitan areas across the globe. Catalytic converters containing supported catalysts and particulate filters have been used to remove such harmful pollutants from the vehicle exhaust. While pollution from vehicle exhaust has decreased over the years from the use of catalytic converters and particulate filters, research into improved supported catalysts has been continuing as requirements for vehicle emission control have become more stringent and as vehicle manufacturers seek to use less amounts of precious metal in the supported catalysts to reduce the total cost of emission control.

[0005] The prior art teaches the use of supported catalysts containing palladium and gold as good partial oxidation catalysts. As such, they have been used extensively in the production of vinyl acetate in the vapor phase by reaction of ethylene, acetic acid and oxygen. See, e.g., U.S. Patent No. 6,022,823. As for vehicle emission control applications, U.S. Patent No. 6,763,309 speculates that palladium-gold might be a good bimetallic candidate for increasing the rate of NO decomposition. The disclosure, however, is based on a mathematical model and is not supported by experimental data. There is also no teaching in this patent that a palladium-gold system will be effective in treating vehicle emissions that include CO and HC.

SUMMARY OF THE INVENTION

[0006] The present invention provides emission control catalysts for treating emissions that include CO and HC, and methods for producing the same. The engine may be a vehicle engine, an industrial engine, or generally, any type of engine that burns hydrocarbons.

[0007] An emission control catalyst according to embodiments of the present invention includes a supported platinum-based catalyst and a supported palladium- gold catalyst. The two catalysts are coated onto different layers, zones, or monoliths of the substrate for the emission control catalyst such that the platinum- based catalyst encounters the exhaust stream before the palladium-gold catalyst. Zeolite may be added to the emission control catalyst as a hydrocarbon absorbing component to boost the oxidation activity of the palladium-gold catalyst.

[0008] The inventors have enabled the use of supported catalysts comprising palladium and gold species as emission control catalysts by overcoming the problem which they have discovered through tests that HC species present in the exhaust inhibit the oxidation activity of such catalysts. With the present invention, such HC inhibition effects are reduced sufficiently by exposing the exhaust to the platinum-based catalyst before the palladium-gold catalyst and/or by adding a hydrocarbon absorbing material, so that the oxidation activity of the palladium-gold catalyst can be improved and the overall catalytic activity of the emission control catalyst can be boosted to effective levels. The inventors have confirmed through vehicle performance tests that the emission control catalysts according to embodiments of the present invention perform as well as platinum-palladium catalysts in reducing CO and HC emissions from a vehicle.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

[0010] FIGS. 1A-1 D are schematic representations of different engine exhaust systems in which embodiments of the present invention may be used.

[0011] FIG. 2 is an illustration of a catalytic converter with a cut-away section that shows a substrate onto which emission control catalysts according to embodiments of the present invention are coated. [0012] FIGS. 3A-3D illustrate different configurations of a substrate for an emission control catalyst.

[0013] Figure 4 is a flow diagram illustrating the steps for preparing an emission control catalyst according to an embodiment of the present invention.

[0014] Figure 5 is a flow diagram illustrating the steps for preparing an emission control catalyst according to another embodiment of the present invention.

DETAILED DESCRIPTION

[0015] In the following, reference is made to embodiments of the invention. However, it should be understood that the invention is not limited to specific described embodiments. Instead, any combination of the following features and elements, whether related to different embodiments or not, is contemplated to implement and practice the invention. Furthermore, in various embodiments the invention provides numerous advantages over the prior art. However, although embodiments of the invention may achieve advantages over other possible solutions and/or over the prior art, whether or not a particular advantage is achieved by a given embodiment is not limiting of the invention. Thus, the following aspects, features, embodiments and advantages are merely illustrative and are not considered elements or limitations of the appended claims except where explicitly recited in the claims. Likewise, reference to "the invention" shall not be construed as a generalization of any inventive subject matter disclosed herein and shall not be considered to be an element or limitation of the appended claims except where explicitly recited in the claims.

[0016] Figures 1A-1 D are schematic representations of different engine exhaust systems in which embodiments of the present invention may be used. The combustion process that occurs in an engine 102 produces harmful pollutants, such as CO, various hydrocarbons, particulate matter, and nitrogen oxides (NOx), in an exhaust stream that is discharged through a tail pipe 108 of the exhaust system.

[0017] In the exhaust system of Figure 1A, the exhaust stream from an engine 102 passes through a catalytic converter 104, before it is discharged into the atmosphere (environment) through a tail pipe 108. The catalytic converter 104 contains supported catalysts coated on a monolithic substrate that treat the exhaust stream from the engine 102. The exhaust stream is treated by way of various catalytic reactions that occur within the catalytic converter 104. These reactions include the oxidation of CO to form CO2, burning of hydrocarbons, and the conversion of NO to NO2.

[0018] In the exhaust system of Figure 1 B, the exhaust stream from the engine 102 passes through a catalytic converter 104 and a particulate filter 106, before it is discharged into the atmosphere through a tail pipe 108. The catalytic converter 104 operates in the same manner as in the exhaust system of Figure 1A. The particulate filter 106 traps particulate matter that is in the exhaust stream, e.g., soot, liquid hydrocarbons, generally particulates in liquid form. In an optional configuration, the particulate filter 106 includes a supported catalyst coated thereon for the oxidation of NO and/or to aid in combustion of particulate matter.

[0019] In the exhaust system of Figure 1C, the exhaust stream from the engine 102 passes through a catalytic converter 104, a pre-filter catalyst 105 and a particulate filter 106, before it is discharged into the atmosphere through a tail pipe 108. The catalytic converter 104 operates in the same manner as in the exhaust system of Figure 1A. The pre-filter catalyst 105 includes a monolithic substrate and supported catalysts coated on the monolithic substrate for the oxidation of NO. The particulate filter 106 traps particulate matter that is in the exhaust stream, e.g., soot, liquid hydrocarbons, generally particulates in liquid form.

[0020] In the exhaust system of Figure 1 D, the exhaust stream passes from the engine 102 through a catalytic converter 104, a particulate filter 106, a selective catalytic reduction (SCR) unit 107 and an ammonia slip catalyst 110, before it is discharged into the atmosphere through a tail pipe 108. The catalytic converter 104 operates in the same manner as in the exhaust system of Figure 1A. The particulate filter 106 traps particulate matter that is in the exhaust stream, e.g., soot, liquid hydrocarbons, generally particulates in liquid form. In an optional configuration, the particulate filter 106 includes a supported catalyst coated thereon for the oxidation of NO and/or to aid in combustion of particulate matter. The SCR unit 107 is provided to reduce the NOx species to N2. The SCR unit 107 may be ammonia/urea based or hydrocarbon based. The ammonia slip catalyst 110 is provided to reduce the amount of ammonia emissions through the tail pipe 108. An alternative configuration places the SCR unit 107 in front of the particulate filter 106.

[0021] Alternative configurations of the exhaust system includes the provision of SCR unit 107 and the ammonia slip catalyst 110 in the exhaust system of Figure 1A or 1C, and the provision of just the SCR unit 107, without the ammonia slip catalyst 110, in the exhaust system of Figures 1A, 1 B or 1C.

[0022] As particulates get trapped in the particulate filter within the exhaust system of Figure 1 B, 1C or 1 D, it becomes less effective and regeneration of the particulate filter becomes necessary. The regeneration of the particulate filter can be either passive or active. Passive regeneration occurs automatically in the presence of NO2. Thus, as the exhaust stream containing NO2 passes through the particulate filter, passive regeneration occurs. During regeneration, the particulates get oxidized and NO2 gets converted back to NO. In general, higher amounts of NO2 improve the regeneration performance, and thus this process is commonly referred to as NO2 assisted oxidation. However, too much NO2 is not desirable because excess NO2 is released into the atmosphere and NO2 is considered to be a more harmful pollutant than NO. The NO2 used for regeneration can be formed in the engine during combustion, from NO oxidation in the catalytic converter 104, from NO oxidation in the pre-filter catalyst 105, and/or from NO oxidation in a catalyzed version of the particulate filter 106.

[0023] Active regeneration is carried out by heating up the particulate filter 106 and oxidizing the particulates. At higher temperatures, NO2 assistance of the particulate oxidation becomes less important. The heating of the particulate filter 106 may be carried out in various ways known in the art. One way is to employ a fuel burner which heats the particulate filter 106 to particulate combustion temperatures. Another way is to increase the temperature of the exhaust stream by modifying the engine output when the particulate filter load reaches a pre-determined level.

[0024] The present invention provides catalysts that are to be used in the catalytic converter 104 shown in FIGS. 1A-1 D, or generally as catalysts in any vehicle emission control system, including as a diesel oxidation catalyst, a diesel filter catalyst, an ammonia-slip catalyst, an SCR catalyst, or as a component of a three- way catalyst. The present invention further provides a vehicle emission control system, such as the ones shown in FIGS. 1A-1 D, comprising an emission control catalyst comprising a monolith and a supported catalyst coated on the monolith.

[0025] FIG. 2 is an illustration of a catalytic converter with a cut-away section that shows a substrate 210 onto which supported metal catalysts are coated. The exploded view of the substrate 210 shows that the substrate 210 has a honeycomb structure comprising a plurality of channels into which washcoats containing supported metal catalysts are flowed in slurry form so as to form coating 220 on the substrate 210.

[0026] FIGS. 3A-3D illustrate different embodiments of the present invention. In the embodiment of FIG. 3A, coating 220 comprises two washcoat layers 221 , 223 on top of substrate 210. Washcoat layer 221 is the bottom layer that is disposed directly on top of the substrate 210 and contains metal particles having palladium and gold in close contact (also referred to as "palladium-gold metal particles"). Washcoat layer 223 is the top layer that is in direct contact with the exhaust stream and contains metal particles having platinum alone or in close contact with another metal species such as palladium (also referred to as "platinum-containing metal particles"). Based on their positions relative to the exhaust stream, washcoat layer 223 encounters the exhaust stream before washcoat layer 221.

[0027] In the embodiment of FIG. 3B, coating 220 comprises three washcoat layers 221 , 222, 223 on top of substrate 210. Washcoat layer 221 is the bottom layer that is disposed directly on top of the substrate 210 and includes palladium-gold metal particles. Washcoat layer 223 is the top layer that is in direct contact with the exhaust stream and includes platinum-containing metal particles. Washcoat layer 222 is the middle layer or buffer layer that is disposed in between washcoat layers 221 , 223. The middle layer is provided to minimize the interaction between the R and Pd-Au components. The middle layer may be a blank support or may contain zeolites, rare earth oxides, inorganic oxides, and/or supported palladium particles. Based on their positions relative to the exhaust stream, washcoat layer 223 encounters the exhaust stream before washcoat layers 221 , 222, and washcoat layer 222 encounters the exhaust stream before washcoat layer 221.

[0028] In the embodiment of FIG. 3C, the substrate 210 is a single monolith that has two coating zones 210A, 210B. A washcoat including platinum-containing metal particles is coated onto a first zone 210A and a washcoat including palladium-gold metal particles is coated onto a second zone 210B.

[0029] In the embodiment of FIG. 3D, the substrate 210 includes first and second monoliths 231 , 232, which are physically separate monoliths. A washcoat including platinum-containing metal particles is coated onto the first monolith 231 and a washcoat including palladium-gold metal particles is coated onto the second monolith 232.

[0030] All of the embodiments described above include a palladium-gold catalyst in combination with a platinum-based catalyst. The weight ratio of palladium to gold in the palladium-gold catalyst is about 0.05:1 to 20:1 , preferably from about 0.5:1 to about 2:1. The palladium-gold catalyst may be promoted with bismuth or other known promoters. The platinum-based catalyst may be a platinum catalyst, a platinum-palladium catalyst, a platinum catalyst promoted with bismuth or other known promoters, or other platinum-based catalysts (e.g., Pt-Rh, Pt-Ir, Pt-Ru, Pt- Au, Pt-Ag, Pt-Rh-Ir, Pt-Ir-Au, etc.). The preferred embodiments employ a platinum- palladium catalyst as the platinum-based catalyst. The weight ratio of platinum to palladium in this catalyst is about 0.05:1 to 20:1 , preferably from about 2:1 to about 4:1.

[0031] In addition, the platinum-based catalyst is situated so that it encounters the exhaust stream prior to the palladium-gold catalyst. By positioning the platinum- based catalyst relative to the palladium-gold catalyst in this manner, the inventors have discovered that HC inhibition effects on the oxidation activity of the palladium- gold catalyst are reduced to sufficient levels so that the overall catalytic performance is improved. In the embodiments of FIG. 3A and 3B, the platinum- based catalyst is included in the top layer 223 and the palladium-gold catalyst is included in the bottom layer 221. In the embodiment of FIG. 3C, the platinum- based catalyst is included in the first zone 210A and the palladium-gold catalyst is included in the second zone 210B. In the embodiment of FIG. 3D, the platinum- based catalyst is included in the first monolith 231 and the palladium-gold catalyst is included in the second monolith 232.

[0032] In additional embodiments of the present invention, a hydrocarbon absorbing material is added to the emission control catalyst. Preferably, the hydrocarbon absorbing material is added to the emission control catalyst so that it encounters exhaust stream prior to the palladium-gold catalyst. By positioning the hydrocarbon absorbing material relative to the palladium-gold catalyst in this manner, the inventors have discovered that HC inhibition effects on the oxidation activity of the palladium-gold catalyst are reduced to sufficient levels so that the overall catalytic performance is improved. In the configuration shown in FIG. 3A, the hydrocarbon absorbing material may be included in the top layer 223. In the configuration shown in FIG. 3B, the hydrocarbon absorbing material may be included in the middle layer 222 or the top layer 223. In the configuration shown in FIG. 3C, the hydrocarbon absorbing material may be included in the first zone 210A. In the configuration shown in FIG. 3D, the hydrocarbon absorbing material may be included in the front monolith 231. In the examples provided below, a hydrocarbon absorbing material is zeolite. Zeolite may be a beta zeolite, ZSM-5 zeolite, and mixtures of the two, with or without other types of zeolites, in any weight ratio.

[0033] In other embodiments of the present invention, any of the washcoat layers or zones, or monoliths may include rare-earth oxides, such as cerium(IV) oxide (CeOa) and ceria-zirconia (CeO2-ZrO2).

[0034] FIG. 4 is a flow diagram that illustrates the steps for preparing an emission control catalyst according to an embodiment of the present invention using the substrate 210. In step 410, a first supported catalyst, e.g., supported palladium- gold catalyst, is prepared is accordance with known methods or with the methods described in the examples provided below. In step 412, a second supported catalyst, e.g., supported platinum-based catalyst, is prepared in accordance with known methods or with the methods described in the examples provided below. A monolithic substrate, such as substrate 210 shown in FIG. 2 (or monolithic substrates 231 , 232 shown in FIG. 3D) is provided in step 414. Exemplary monolithic substrates include those that are ceramic (e.g., cordierite), metallic, or silicon carbide based. In step 416, the first supported catalyst in powder form are mixed in a solvent to form a washcoat slurry, and the washcoat slurry is coated as the bottom layer of the substrate 210 or onto a rear zone or rear monolith of the substrate 210. In step 418, the second supported catalyst in powder form are mixed in a solvent to form a washcoat slurry, and the washcoat slurry is coated as the top layer of the substrate 210 or onto a front zone or front monolith of the substrate 210. Optionally, zeolite or zeolite mixture including one or more of beta zeolite, ZSM-5 zeolite, and other types of zeolites is added to the washcoat slurry before the washcoat slurry is coated in step 418.

[0035] FIG. 5 is a flow diagram that illustrates the steps for preparing an emission control catalyst according to another embodiment of the present invention using the substrate 210. In step 510, a first supported catalyst, e.g., supported palladium- gold catalyst, is prepared is accordance with known methods or with the methods described in the examples provided below. In step 512, a second supported catalyst, e.g., supported platinum-based catalyst, is prepared in accordance with known methods or with the methods described in the examples provided below. A monolithic substrate, such as substrate 210 shown in FIG. 2, is provided in step 514. Exemplary monolithic substrates include those that are ceramic (e.g., cordierite), metallic, or silicon carbide based. In step 516, the first supported catalyst in powder form are mixed in a solvent to form a washcoat slurry, and the washcoat slurry is coated as the bottom layer of the substrate 210. In step 517, zeolite or zeolite mixture is added to a solvent to form a washcoat slurry and this washcoat slurry is coated as the middle layer of the substrate 210. In step 518, the second supported catalyst in powder form are mixed in a solvent to form a washcoat slurry, and the washcoat slurry is coated as the top layer of the substrate 210.

[0036] The data representing vehicle performance of the various embodiments of the present invention are provided in Tables 1 , 2, 3, and 4.

Table 1

Figure imgf000012_0001

Table 2

Figure imgf000012_0002

Table 3

Figure imgf000012_0003
Table 4

Figure imgf000013_0001

[0037] For the data presented in Tables 1-4, the CO and HC emissions were measured from the tail pipe of a light-duty diesel vehicle (model year 2005) using bag data from the standard European MVEG test. The data presented in Tables 1 and 2 above reflect the vehicle test performance for seven catalysts with equal precious group metal cost (assuming cost basis of Pt:Pd:Au of 4:1 :2) that have been engine aged for 20 hours (with a two-mode cycle using fuel injection to get catalyst bed temperatures of about 650 0C). The data presented in Tables 3 and 4 above reflect the fresh CO oxidation vehicle performance for four catalysts with equal precious group metal cost (assuming cost basis of Pt:Pd:Au of 4:1 :2). Examples of Table 1 were tested under low engine out temperatures (around 150 0C to 300 0C) and Examples of Table 2 were tested under high engine out temperatures (around 200 0C to 350 °C). The catalysts of Examples 1-3 and 11 were coated on a cordierite substrate with a diameter of 5.66 inches and length of 2.5 inches. The catalysts of Examples 4-10 were coated on a pair of cordierite substrates, each with a diameter of 5.66 inches and length of 1.25 inches.

[0038] Table 1 presents data for emission control catalysts having a tri-layer configuration (see FIG. 3B). Example 1 represents a benchmark emission control catalyst and includes metal particles having platinum and palladium in close contact (also referred to as "platinum-palladium metal particles") having a weight ratio of 2.8%:1.4% in the bottom layer and the top layer. The middle layer comprises beta zeolite. Example 2 also represents a benchmark emission control catalyst and has the same composition as Example 1 except the middle layer comprises a zeolite mixture of beta zeolite and ZSM-5 zeolite at a weight ratio of 1 :1. Example 3 represents an emission control catalyst according to an embodiment of the present invention and includes palladium-gold metal particles having a weight ratio of 1.7%:2.0% in the bottom layer and platinum-palladium metal particles having a weight ratio of 3.0%:0.75% in the top layer. The middle layer comprises a zeolite mixture of beta zeolite and ZSM-5 zeolite at a weight ratio of 1 :1. Relative to the benchmark emission control catalysts of Examples 1 and 2, a reduction in both HC and CO emissions has been observed with the emission control catalyst of Example 3.

[0039] Table 2 presents data for emission control catalysts having a dual-brick configuration (see FIG. 3D). Example 4 represents a benchmark emission control catalyst and includes platinum-palladium metal particles having a weight ratio of 2.0%:1.0% in the front brick and the rear brick. Examples 5, 6 and 7 represent emission control catalysts according to embodiments of the present invention, each of which includes palladium-gold metal particles. Example 5 includes platinum- palladium metal particles having a weight ratio of 2.0%:1.0% in the front brick and palladium-gold metal particles having weight ratio of 1.7%:2.0% in the rear brick. Example 6 includes platinum-palladium metal particles having a weight ratio of 4.0%:1.0% in the front brick and palladium-gold metal particles having weight ratio of 1.7%:2.0% in the rear brick. Example 7 includes platinum-palladium metal particles having a weight ratio of 2.0%: 1.0% in the front brick and palladium-gold metal particles having weight ratio of 1.7%:2.0% in the rear brick. Both bricks in Example 7 used a washcoat slurry with approximately 28% ceria-zirconia added in (the rest was the precious group metal and alumina powder). Relative to the benchmark emission control catalyst of Example 4, a reduction in HC emissions and similar or better CO oxidation performance have been observed with the emission control catalysts of Examples 5, 6 and 7.

[0040] The data in Tables 3 and 4 indicate that a performance enhancement is realized in further embodiments of the present invention for catalysts that have not been aged when multiple substrates with a Pt-based catalyst and a Pd-Au catalyst (Examples 9 and 10) or multi-layers of a Pt-based catalyst and a Pd-Au catalyst on a single substrate (Example 11) are employed. It is noted that when the Pt-Pd brick from Example 9 is used in combination with a blank brick in place of the Pd-Au brick (as a control), the performance is not nearly as good (see Example 8) as when the Pd-Au is present. As a further benchmark, the performance of a Pd-Au only system (Pd:Au = 0.85:1.0 by weight at 140 g/ft3) was tested. The CO emissions from that system were observed to be 0.398 g/km.

[0041] Deterioration in the CO oxidation performance has been experimentally observed by the inventors after aging the Pt-based and Pd-Au-containing physically mixed catalysts. When these catalysts are subject to elevated temperatures for prolonged periods of time, beyond the well-known phenomenon of metal sintering, another pathway for performance degradation via sintering and formation of less active ternary alloys (Pt-Pd-Au) in these systems has been discovered. Experimental data show that the deactivation of the engine exhaust catalyst containing a first supported catalyst comprising platinum and a second supported catalyst comprising palladium-gold particles is caused by the formation of a ternary alloy (Pt-Pd-Au).

[0042] FIGS. 3B-3D illustrate three different configurations of a substrate 210 of an engine exhaust catalyst that is designed to suppress these catalyst aging effects and allow maximum performance. The three configurations of the substrate 210 described above suppress the formation of the ternary alloy by keeping the platinum physically separate from palladium-gold. Vehicle CO emission data for examples of some of the above described configurations are shown in Tables 1- 4. It is clear that the benefits of combining a Pt-based catalyst with a Pd-Au catalyst are maintained while the possibility of forming a ternary alloy upon extensive aging has been significantly reduced in the case of multi-layer systems or eliminated completely in the case of multi-brick systems.

[0043] For the tri-layered approach of FIG. 3B, ceria-based materials in the middle layer might further slow down Pt migration and suppress ternary alloy formation. See Nagai, et. al., "Sintering inhibition mechanism of platinum supported on ceria- based oxide and Pt-oxide-support interaction," J. Catal. Vol. 242, pp. 103-109 (2006). A palladium-containing middle layer will allow formation of additional binary alloys upon sintering and slow down the sintering process as alloys tend to sinter less than individual metals. [0044] The preparation methods for Examples 1-11 were as follows:

Preparation of a 1.7% Pd, 2.0% Au supported PdAu catalyst.

[0045] Lanthanum-stabilized alumina (578 g, having a surface area of -200 m2g"1) and 2940 ml_ of de-ionized water (>18MΩ) were added to a 5 L plastic beaker and magnetically stirred at about 500 rpm. The pH measured was 8.5 and the temperature measured was 25 0C. After 20 minutes, Pd(NO3)2 (67.8 g of 14.8% aqueous solution) was gradually added over a period of 10 min. The pH measured was 4.3. After stirring for 20 minutes, a second metal, HAuCI4 (24 g dissolved in 50 ml_ of de-ionized water), was added over a period of 5 min. The pH was 4.0 and the temperature of the metal-support slurry was 25 °C. The metal-support slurry was stirred for an additional 30 min. In a second vessel, NaBH4 (29.4 g) and NaOH (31.1 g) were added to N2H4 (142 ml_ of 35% aqueous solution) and stirred until the mixture became clear. This mixture constituted the reducing agent mixture. The metal-support slurry and reducing agent mixture were combined continuously using two peristaltic pumps. The two streams were combined using a Y joint connected to a Vigreux column to cause turbulent mixing. The reaction product leaving the mixing chamber, i.e., the Vigreux column, was pumped into an intermediate vessel of smaller volume and continuously stirred. The product in the intermediate vessel was continuously pumped into a larger vessel, i.e., 5 L beaker, for residence and with continued stirring. The entire addition/mixing process lasted about 30 min. The resulting product slurry was stirred in the larger vessel for an additional period of 1 h. The final pH was 11.0 and the temperature was 25 0C. The product slurry was then filtered using vacuum techniques via Buchner funnels provided with a double layer of filter paper having 3 μm porosity. The filter cake was then washed with about 20 L of de-ionized water in several approximately equal portions. Thereafter, the washed cake was dried at 110 0C, ground to a fine powder using a mortar and pestle, and subsequently calcined at 500 0C for 2 h, with a heating rate of 8 0C min"1. This supported PdAu catalyst powder (1.7% Pd, 2.0% Au) was used in preparing Examples 3, 5, 6, 7, 9, 10, and 11. Preparation of a 2.8% Pt, 1.4% Pd supported catalyst.

[0046] To 10 L of de-ionized H2O was added 1940 g of La-stabilized alumina (having a BET surface area of -200 m2 g"1) followed by stirring for 30 minutes at room temperature. To this slurry was added 490.6 g of Pt(NOe)2 solution (12.23% Pt(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. Acrylic acid (750 ml_, 99% purity) was then added into the system over 12 minutes and the resulting mixture was allowed to continue stirring at room temperature for 2 hours. The solid La-doped alumina supported Pt catalyst was separated from the liquid via filtration, dried at 120 °C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a 3% Pt material.

[0047] To 9.25 L of de-ionized H2O was added 1822 g of the above 3% Pt material followed by stirring for 20 minutes at room temperature. To this slurry was added 194.4 g of Pd(NO3)2 solution (14.28% Pd(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. An aqueous ascorbic acid solution (930 g in 4.5 L of de-ionized H2O) was then added over 25 minutes followed by stirring for 60 minutes. The solid La-doped alumina supported PtPd catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a 3% Pt, 1.5% Pd material. This material was diluted to 2.8% Pt, 1.4% Pd via addition of blank La-doped alumina support and the diluted mixture was used in preparing Examples 1 , 2, 8, 9, and 11.

Preparation of a 2.0% Pt, 1.0% Pd supported catalyst.

[0048] To 10 L of de-ionized H2O was added 2000 g of La-stabilized alumina (having a BET surface area of -200 m2 g~1) followed by stirring for 30 minutes at room temperature. To this slurry was added 327.1 g of Pt(NO3)2 solution (12.23% Pt(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. Acrylic acid (500 mL, 99% purity) was then added into the system over 12 minutes and the resulting mixture was allowed to continue stirring at room temperature for 2 hours. The solid La-doped alumina supported Pt catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a 2% Pt material.

[0049] To 9.5 L of de-ionized H2O was added 1900 g of the above 2% Pt material followed by stirring for 20 minutes at room temperature. To this slurry was added 135.3 g of Pd(NO3)2 solution (14.28% Pd(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. An aqueous ascorbic acid solution (647.2 g in 3.5 L of de-ionized H2O) was then added over 25 minutes followed by stirring for 60 minutes. The solid La-doped alumina supported PtPd catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 0C min"1) to give a 2% Pt, 1% Pd material. This material was used in preparing Examples 4, 5 and 7.

Preparation of a 3.0% Pt, 0.75% Pd supported catalyst

[0050] To 10 L of de-ionized H2O was added 2000 g of La-stabilized alumina (having a BET surface area of -200 m2 g"1) followed by stirring for 30 minutes at room temperature. To this slurry was added 654.2 g of Pt(NOs)2 solution (12.23% Pt(NO3);? by weight), followed by stirring at room temperature for 60 minutes. Acrylic acid (500 mL, 99% purity) was then added into the system over 12 minutes and the resulting mixture was allowed to continue stirring at room temperature for 2 hours. The solid La-doped alumina supported Pt catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a 4% Pt material.

[0051] To 9.5 L of de-ionized H2O was added 3800 g of the above 4% Pt material followed by stirring for 20 minutes at room temperature. To this slurry was added 135.3 g of Pd(NO3)2 solution (14.28% Pd(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. An aqueous ascorbic acid solution (647.2 g in 3.5 L of de-ionized H2O) was then added over 25 minutes followed by stirring for 60 minutes. The solid La-doped alumina supported PtPd catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a 4% Pt, 1% Pd material. This material was then diluted to 3.0% Pt, 0.75% Pd via addition of blank La-doped alumina support and the diluted mixture was used in preparing Examples 3 and 6.

Preparation of a 3.0% Pt, 2.0% Bi supported catalyst.

[0052] To 10 L of de-ionized H2O was added 2000 g of La-stabilized alumina (having a BET surface area of -200 m2 g"1) followed by stirring for 30 minutes at room temperature. To this slurry was added 436.1 g of Pt(NOa)2 solution (13.76% Pt(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. Acrylic acid (750 mL, 99% purity) was then added into the system over 12 minutes and the resulting mixture was allowed to continue stirring at room temperature for 2 hours. The solid La-doped alumina supported Pt catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1).

[0053] To 1600 g of the La-stabilized alumina supported 3% Pt catalyst prepared above was added a solution of bismuth acetate (59.1 g of bismuth acetate in 1.4 L of de-ionized H2O and 0.25 L of glacial acetic acid). The resulting paste was mechanically mixed at room temperature for 10 minutes, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) providing the final supported 3.0% Pt, 2.0% Bi catalyst used in preparing Example 10.

Preparation of a 3.0% Pd supported catalyst.

[0054] To 5 L of de-ionized H2O was added 1000 g of a rare-earth oxide support (ceria-zirconia based with a surface area of -90 m2 g"1) followed by stirring for 20 minutes at room temperature. To this slurry was added 211.8 g of Pd(NOa)2 solution (14.28% Pd(NO3)2 by weight), followed by stirring at room temperature for 60 minutes. An aqueous ascorbic acid solution (1013 g in 5 L of deionized H2O) was then added over 25 minutes followed by stirring for 60 minutes. The solid La-doped alumina supported PtPd catalyst was separated from the liquid via filtration, dried at 120 0C for 2 hours, ground into a fine powder, and calcined in air for 2 hours at a temperature of 500 0C (heated at 8 °C min"1) to give a supported 3% Pd material. This material was used in preparing Example 11.

Example 1 - Tri-layer: PtPd (at 57.5 g/ft3) 1st layer, beta zeolite 2nd layer, PtPd (at 57.5 g/ft3) 3rd layer.

[0055] The supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 2.5 inches), dried at 120 °C and calcined at 500 0C to give the first layer of the multi-layer coated monolith, such that the PtPd loading was -57.5 g/ft3.

[0056] Then, beta zeolite was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the zeolite washcoat slurry was coated onto the cordierite monolith (with the first layer of PtPd), dried at 120 °C and calcined at 500 °C to give the second layer of the multi-layer coated monolith. The zeolite mixture comprises about 20% of the total washcoat loading.

[0057] Then, the supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto the cordierite monolith (with the first layer of PtPd and the second layer of zeolite), dried at 120 °C and calcined at 500 °C to give the third layer of the multi-layer coated monolith, such that the PtPd loading was -57.5 g/ft3 . [0058] The multi-layer coated monolith was canned according to methods known in the art and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 2 - Tri-layer: PtPd (at 57.5 g/ft3) 1st layer, zeolite mixture 2nd layer, PtPd (at 57.5 g/ft3) 3rd layer.

[0059] The supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 2.5 inches), dried at 120 0C and calcined at 500 0C to give the first layer of the multi-layer coated monolith, such that the PtPd loading was -57.5 g/ft3.

[0060] Then, equal weight amounts of a beta zeolite and a ZSM-5 zeolite were combined and made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the zeolite washcoat slurry was coated onto the cordierite monolith (with the first layer of PtPd)1 dried at 120 °C and calcined at 500 0C to give the second layer of the multi-layer coated monolith. The zeolite mixture comprises about 20% of the total washcoat loading.

[0061] Then, the supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto the cordierite monolith (with the first layer of PtPd and the second layer of zeolite), dried at 120 °C and calcined at 500 °C to give the third layer of the multi-layer coated monolith, such that the PtPd loading was -57.5 g/ft3 . [0062] The multi-layer coated monolith was canned according to methods known in the art and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 3 - PdAu (at 65 g/ft3) 1st layer, zeolite mixture 2nd layer, PtPd (at 65 g/ft3) 3rd layer.

[0063] The supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 2.5 inches), dried at 120 °C and calcined at 500 0C to give the first layer of the multi-layer coated monolith, such that the PdAu loading was -65 g/ft3.

[0064] Then, equal weight amounts of a beta zeolite and a ZSM-5 zeolite were combined and made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the zeolite washcoat slurry was coated onto the cordierite monolith (with the first layer of PtPd), dried at 120 °C and calcined at 500 0C to give the second layer of the multi-layer coated monolith. The zeolite mixture comprises about 20% of the total washcoat loading.

[0065] Then, the supported PtPd catalyst powder (3.0% Pt, 0.75% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto the cordierite monolith (with the first layer of PdAu and the second layer of zeolite), dried at 120 0C and calcined at 500 °C to give the third layer of the multi-layer coated monolith, such that the PtPd loading was -65 g/ft3. [0066] The multi-layer coated monolith was canned according to methods known in the art and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 4 - Multi-brick: Pt/Pd at 120 g/ft3

[0067] The supported PtPd catalyst powder (2.0% Pt, 1.0% Pd) prepared above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto both the front brick and the rear brick of a round cordierite monolith (each brick: Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 0C to give the final coated monolith with a precious metal (Pt + Pd) loading of 120 g/ft3. The coated monolith was canned according to methods known in the art and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 5 - Multi-brick: Pt/Pd (at 120 g/ft3) front and PdAu (at 175 g/ft3) rear

[0068] The supported PtPd catalyst powder (2.0% Pt, 1.0% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 120 g/ft3 PtPd. This represented the front brick of a two brick system.

[0069] In addition, the supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 175 g/ft3 PdAu. This represented the outlet brick of a two brick system.

[0070] The coated PtPd monolith (front brick) and the coated PdAu monolith (rear brick) were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 6 - Multi-brick: Pt/Pd (at 130 g/ft3) front and PdAu (at 130 g/ft3) rear

[00711 The supported PtPd catalyst powder (3.0% Pt, 0.75% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 130 g/ft3 PtPd. This represented the front brick of a two brick system.

[0072] In addition, the supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 130 g/ft3 PdAu. This represented the outlet brick of a two brick system.

[0073] The coated PtPd monolith (front brick) and the coated PdAu monolith (rear brick) were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above. Example 7 - Multi-brick: Pt/Pd (at 150 g/ft3) front and PdAu (at 130 g/ft3) rear

[0074] The supported PtPd catalyst powder (2.0% Pt, 1.0% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. Ceria-zirconia was added to this washcoat slurry so that ceria-zirconia represented about 28% by weight. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 0C and calcined at 500 0C to give the final coated monolith with a precious metal loading of 150 g/ft3 PtPd. This represented the front brick of a two brick system.

[0075] In addition, the supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. Ceria-zirconia was added to this washcoat slurry so that ceria-zirconia represented about 28% by weight. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 0C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 130 g/ft3 PdAu. This represented the outlet brick of a two brick system.

[0076] The coated PtPd monolith (front brick) and the coated PdAu monolith (rear brick) were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 8 - Multi-brick control: Pt/Pd (at 170 g/ft3) front and a blank rear

[0077] The supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 0C to give the final coated monolith with a precious metal loading of 170 g/ft3 PtPd. This represented the front brick of a two brick system. In addition, a blank cordierite monolith of equal size (Corning, 400 cpsi, 5.66 inches X 1.25 inches) was designated as the rear brick. The coated monolith and the blank brick were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 9 - Multi-brick: Pt/Pd (at 170 g/ft3) front and PdAu (at 146 g/ft 3) rear

[0078] The supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 0C to give the final coated monolith with a precious metal loading of 170 g/ft3 PtPd. This represented the front brick of a two brick system.

[0079] In addition, the supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 0C and calcined at 500 0C to give the final coated monolith with a precious metal loading of 146 g/ft3 PdAu. This represented the rear brick of a two brick system. [0080] The coated PtPd monolith (front brick) and the coated PdAu monolith (rear brick) were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above.

Example 10 - Multi-brick: PtBi (at 120 g/ft3) front and PdAu (at 146 g/ft3) rear

[0081] The supported PtBi catalyst powder (3.0% Pt, 2.0% Bi) prepared as described above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 0C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 120 g/ft3 Pt. This represented the front brick of a two brick system.

[0082] In addition, the supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared as described above was made into a washcoat slurry via addition to de- ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 1.25 inches), dried at 120 °C and calcined at 500 °C to give the final coated monolith with a precious metal loading of 146 g/ft3 PdAu. This represented the rear brick of a two brick system.

[0083] The coated PtBi monolith (front brick) and the coated PdAu monolith (rear brick) were then canned according to methods known in the art such that the front brick was closest to the engine (and hence would be exposed to the exhaust first), and tested using a certified testing facility on a light-duty diesel vehicle, as described above. Example 11 - Multi-layer: PdAu (at 73 g/ft3) 1st layer, Pd (at 30 g/ft3) 2nd layer, PtPd (at 85 g/ft3) 3rd layer.

[0084] The supported PdAu catalyst powder (1.7% Pd, 2.0% Au) prepared above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the washcoat slurry was coated onto a round cordierite monolith (Corning, 400 cpsi, 5.66 inches X 2.5 inches), dried at 120 °C and calcined at 500 0C to give the first layer of the multi-layer coated monolith.

[0085] Then, the supported Pd catalyst powder (3.0% Pd) prepared above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size (typically with a d50 range from 3 to 7 μm), and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the Pd washcoat slurry was coated onto the multi-layer coated cordierite monolith (with the 1st layer of PdAu) such that the Pd loading was -30 g/ft3 after appropriate drying at 120 °C and calcination at 500 °C to give the second layer of the multi-layer coated monolith.

[0086] Then, the supported PtPd catalyst powder (2.8% Pt, 1.4% Pd) prepared above was made into a washcoat slurry via addition to de-ionized water, milling to an appropriate particle size, and pH adjustment to give an appropriate viscosity for washcoating. According to methods known in the art, the PtPd washcoat slurry was coated onto the multi-layer coated cordierite monolith (with the 1st layer of PdAu and the 2nd layer of Pd) such that the PtPd loading was -85 g/ft3 after appropriate drying at 120 0C and calcination at 500 °C to give the third layer of the multi-layer coated monolith.

[0087] The resulting multi-layer (tri-layer in this case) coated monolith had precious metal loadings of 73 g/ft3 PdAu (1st layer), 30 g/ft3 Pd (2nd layer), and 85 g/ft3 PtPd (3rd layer). The multi-layer coated monolith was canned according to methods known in the art and tested using a certified testing facility on a light-duty diesel vehicle, as described above. [0088] While particular embodiments according to the invention have been illustrated and described above, those skilled in the art understand that the invention can take a variety of forms and embodiments within the scope of the appended claims.

Claims

What is claimed is:
1. An emission control catalyst for treating an engine exhaust comprising a first catalytically active zone and a second catalytically active zone, wherein the first catalytically active zone is positioned to encounter the engine exhaust before the second catalytically active zone, and wherein the first catalytically active zone includes a first supported catalyst comprising platinum-containing metal particles supported on an oxide carrier and the second catalytically active zone includes a second supported catalyst consisting essentially of palladium-gold metal particles supported on an oxide carrier.
2. The emission control catalyst according to claim 1 , further comprising a substrate having a honeycomb structure with gas flow channels, wherein the first supported catalyst and the second supported catalyst are coated on the walls of the gas flow channels.
3. The emission control catalyst according to claim 2, wherein multiple layers are coated on the walls of the gas flow channels, and a bottom layer that is directly above the walls of the gas flow channels includes the second supported catalyst and a top layer that is positioned to be in direct contact with the engine exhaust includes the first supported catalyst.
4. The emission control catalyst according to claim 3, wherein the first supported catalyst comprises platinum-palladium metal particles.
5. The emission control catalyst according to claim 3, wherein the top layer further includes zeolite.
6. The emission control catalyst according to claim 3, wherein the multiple layers further include a middle layer between the bottom layer and the top layer.
7. The emission control catalyst according to claim 6, wherein the middle layer comprises zeolite.
8. The emission control catalyst according to claim 1 , further comprising a substrate having an upstream zone and a downstream zone, the upstream zone being positioned to encounter the engine exhaust before the downstream zone, wherein the first supported catalyst is coated on the upstream zone of the substrate and the second supported catalyst is coated on the downstream zone of the substrate.
9. The emission control catalyst according to claim 1 , further comprising an upstream monolith and a downstream monolith, the upstream monolith being positioned to encounter the engine exhaust before the downstream monolith, wherein the first supported catalyst is coated on the upstream monolith and the second supported catalyst is coated on the downstream monolith.
10. An emission control catalyst for treating an engine exhaust comprising a substrate having a first washcoat metal particles comprising platinum and a second washcoat containing metal particles consisting essentially of palladium and gold, wherein the first washcoat is positioned to encounter the engine exhaust prior to the second washcoat.
11. The emission control catalyst according to claim 10, wherein the first washcoat further includes zeolite.
12. The emission control catalyst according to claim 10, further comprising a third washcoat containing zeolite.
13. The emission control catalyst according to claim 10, wherein the substrate has a honeycomb structure with gas flow channels and multiple layers of washcoats are coated on the walls of the gas flow channels, and wherein a bottom layer that is directly in contact with the walls of the gas flow channels includes the second washcoat and a top layer that is positioned to be in direct contact with the engine exhaust includes the first washcoat.
14. The emission control catalyst according to claim 13, wherein the multiple layers include a middle layer between the bottom layer and the top layer, and the middle layer includes a third washcoat containing zeolite.
15. The emission control catalyst according to claim 10, wherein the substrate has an upstream zone and a downstream zone, the upstream zone being positioned to encounter the engine exhaust before the downstream zone, and wherein the first washcoat is coated on the upstream zone of the substrate and the second washcoat is coated on the downstream zone of the substrate.
16. The emission control catalyst according to claim 10, wherein the substrate has an upstream monolith and a downstream monolith, and wherein the first washcoat is coated on the upstream monolith of the substrate and the second washcoat is coated on the downstream monolith of the substrate.
17. An emission control catalyst comprising a first catalyst comprising platinum- containing metal particles, a second catalyst comprising palladium-gold containing metal particles other than platinum-palladium-gold metal particles, and physically separate zones for each of the first catalyst and the second catalyst.
18. The emission control catalyst according to claim 17, further comprising a buffer zone between the physically separate zones for the first catalyst and the second catalyst.
19. The emission control catalyst according to claim 17, wherein the first catalyst comprises a platinum-palladium catalyst having a Pt:Pd weight ratio of 2:1 to 4:1 , and the second catalyst has a Pd:Au weight ratio of 0.5:1 to 2:1.
20. The emission control catalyst according to claim 19, further comprising a zeolite mixture having beta zeolite and ZSM-5 zeolite having a weight ratio of about 1 :1.
PCT/US2007/088085 2006-11-27 2007-12-19 Engine exhaust catalysts containing palladium-gold WO2008088649A1 (en)

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US11/624,116 US20080125313A1 (en) 2006-11-27 2007-01-17 Engine Exhaust Catalysts Containing Palladium-Gold
US11/624,128 2007-01-17
US11/624,116 2007-01-17
US11/624,128 US7709414B2 (en) 2006-11-27 2007-01-17 Engine exhaust catalysts containing palladium-gold
US11/942,710 US7534738B2 (en) 2006-11-27 2007-11-20 Engine exhaust catalysts containing palladium-gold
US11/942,710 2007-11-20

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KR1020097016749A KR101051874B1 (en) 2007-01-17 2007-12-19 Palladium-engine exhaust catalysts containing gold
EP07869495A EP2106291A4 (en) 2007-01-17 2007-12-19 Engine exhaust catalysts containing palladium-gold
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JP5226633B2 (en) 2013-07-03
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EP2106291A4 (en) 2011-10-26
EP2106291A1 (en) 2009-10-07
KR101051874B1 (en) 2011-07-25
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JP2010516445A (en) 2010-05-20
KR20090101377A (en) 2009-09-25

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