US20090324468A1 - Zero platinum group metal catalysts - Google Patents

Zero platinum group metal catalysts Download PDF

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Publication number
US20090324468A1
US20090324468A1 US12/215,694 US21569408A US2009324468A1 US 20090324468 A1 US20090324468 A1 US 20090324468A1 US 21569408 A US21569408 A US 21569408A US 2009324468 A1 US2009324468 A1 US 2009324468A1
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US
United States
Prior art keywords
catalyst system
catalyst
oxide
group
mixtures
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Abandoned
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US12/215,694
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English (en)
Inventor
Stephen J. Golden
Randal Hatfield
Jason Pless
Johnny Ngo
Mann Sakbodin
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Catalytic Solutions Inc
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Catalytic Solutions Inc
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Application filed by Catalytic Solutions Inc filed Critical Catalytic Solutions Inc
Priority to US12/215,694 priority Critical patent/US20090324468A1/en
Priority to US12/229,729 priority patent/US8496896B2/en
Assigned to CATALYTIC SOLUTIONS, INC. reassignment CATALYTIC SOLUTIONS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOLDEN, STEPHEN J., HATFIELD, RANDAL, NGO, JOHNNY, PLESS, JASON, SAKBODIN, MANN
Priority to AU2009263034A priority patent/AU2009263034A1/en
Priority to CN2009801051101A priority patent/CN101939084A/zh
Priority to CA2729235A priority patent/CA2729235A1/fr
Priority to CA2729232A priority patent/CA2729232A1/fr
Priority to KR1020107010963A priority patent/KR101569946B1/ko
Priority to PCT/US2009/003800 priority patent/WO2009158009A1/fr
Priority to JP2011516310A priority patent/JP5010049B2/ja
Priority to MX2011000105A priority patent/MX2011000105A/es
Priority to EP09770547A priority patent/EP2303454A4/fr
Priority to EP09770546A priority patent/EP2303433A4/fr
Priority to AU2009263035A priority patent/AU2009263035A1/en
Priority to JP2011516309A priority patent/JP4950359B2/ja
Priority to CN200980105008.1A priority patent/CN101939097B/zh
Priority to PCT/US2009/003799 priority patent/WO2009158008A1/fr
Priority to MX2011000020A priority patent/MX335990B/es
Priority to KR1020107010982A priority patent/KR101508799B1/ko
Publication of US20090324468A1 publication Critical patent/US20090324468A1/en
Priority to US12/791,699 priority patent/US8685352B2/en
Assigned to ENERTECH CAPITAL PARTNERS II L.P. (AS COLLATERAL AGENT) reassignment ENERTECH CAPITAL PARTNERS II L.P. (AS COLLATERAL AGENT) SECURITY AGREEMENT Assignors: CATALYTIC SOLUTIONS, INC.
Assigned to CATALYTIC SOLUTIONS, INC., ECS HOLDINGS, INC. reassignment CATALYTIC SOLUTIONS, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: ENERTECH CAPITAL PARTNERS II L.P. (AS COLLATERAL AGENT)
Abandoned legal-status Critical Current

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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    • 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
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    • 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
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    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to catalysts which are free of any platinum group metals for reducing emissions of nitrous oxide, carbon monoxide, hydrocarbons, and sulfur in exhaust streams.
  • Catalysts in catalytic converters have been used to decrease the pollution caused by exhaust from various sources, such as automobiles, utility plants, processing and manufacturing plants, airplanes, trains, all terrain vehicles, boats, mining equipment, and other engine-equipped machines.
  • a common catalyst used in this way is the three-way catalyst (“TWC”).
  • the TWC works by converting carbon monoxide, hydrocarbons, and nitrogen oxides into less harmful compounds or pollutants.
  • a TWC works by simultaneously reducing the nitrogen oxides to nitrogen and oxygen, oxidizing carbon monoxide to less harmful carbon dioxide, and oxidizing unburnt hydrocarbons to carbon dioxide and water.
  • the prior art TWC is made using at least some platinum group metals. Platinum group metals are defined in this specification to mean platinum, palladium, ruthenium, iridium, osmium, and rhodium in this application unless otherwise stated.
  • the present invention pertains to a catalyst system comprising a substrate and a washcoat, wherein the catalyst system is substantially free of platinum group metals.
  • the washcoat comprises at least one oxide solid, wherein the oxide solid is selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof.
  • the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof.
  • the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.
  • the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttirum, lanthanides, actinides, and mixtures thereof.
  • the catalyst system may optionally comprise an overcoat comprising at least one oxide solid, wherein the overcoat oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.
  • the present invention also pertains to a catalyst system comprising a substrate, a washcoat, and an overcoat, wherein the catalyst system is substantially free of platinum group metals.
  • the washcoat comprises one or more selected from the group consisting of a carrier material oxide, ceramic, and mixtures thereof.
  • the overcoat comprises a catalyst.
  • the catalyst of the overcoat comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof.
  • the catalyst system may further comprise one or more selected from the group consisting of a perovskite, a spinel, a lyonsite, an oxygen storage material, alumina, and mixtures thereof.
  • a ZPGM transition metal catalyst comprises one or more transition metals.
  • a mixed metal oxide catalyst comprises a mixed metal oxide and at least one transition metal, wherein the mixed metal oxide comprises one or more selected from the group consisting of alkali metals, alkaline earth metals, lanthanides, actinides, and mixtures thereof.
  • a zeolite catalyst comprises at least one zeolite and at least one transition metal. The zeolite comprises one or more selected from the group consisting of ZSM5, heulandite, chabazite, and mixtures thereof.
  • the transition metal comprises one or more selected from the group consisting of chromium, gallium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof
  • the present invention also pertains to a method of making a catalyst system by impregnation, comprising depositing a washcoat on a substrate and treating the washcoat and the substrate to convert metal salts into metal oxides, wherein the catalyst system is substantially free of platinum group metals.
  • the washcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.
  • the method may further comprise after treating, depositing an overcoat on the washcoat and treating the overcoat and washcoat.
  • the overcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.
  • the present invention also pertains to a method of making a catalyst system by precipitation, comprising precipitating a transition metal salt on a washcoat, treating the precipitated transition metal salt and the washcoat, depositing the precipitated transition metal salt and the washcoat on a substrate, and treating the precipitated transition metal salt and the washcoat on the substrate, wherein the catalyst system is substantially free of platinum group metals.
  • the transition metal salt comprises at least one transition metal and at least one carrier material oxide.
  • the method may further comprise after treating the precipitated transition metal salt and the washcoat on the substrate, depositing an overcoat on the treated precipitated transition metal salt and the washcoat, and treating the overcoat, the treated precipitated transition metal salt and the washcoat.
  • the present invention also pertains to a method of making a catalyst system by co-milling, comprising milling together a catalyst and at least one carrier material oxide, depositing the milled catalyst in the form of a washcoat on to a substrate; and treating the substrate and the washcoat, wherein the catalyst system is substantially free of platinum group metals.
  • the method may further comprise depositing an overcoat on the washcoat and treating the overcoat and the washcoat.
  • the overcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.
  • the present invention also pertains to a method of reducing pollutants including, but not limited to nitrogen oxide, carbon monoxide, hydrocarbons, and sulfur emitted in exhaust comprising flowing exhaust substantially through a catalyst system as described herein and reducing the pollutants in the exhaust.
  • the present invention also pertains to a catalyst system comprising a first catalyst system and a second catalyst system.
  • the first catalyst system comprises a substrate and a washcoat, wherein the washcoat comprises at least one oxide solid and wherein the first catalyst system is substantially free of platinum group metals.
  • the second catalyst system comprises at least one platinum group metal.
  • the first and second catalyst systems are in series in any order, wherein at least a substantial portion of a gas stream passes through the first catalyst and the second catalyst sequentially. More than a first and second catalyst system may be used in a catalyst system, e.g. a third catalyst system or more.
  • FIG. 1 shows a schematic of Architecture 1 for the catalyst systems of the present invention
  • FIG. 2 shows a schematic of Architecture 2 for the catalyst systems of the present invention
  • FIG. 3 shows a schematic of Architecture 3 for the catalyst systems of the present invention
  • FIG. 4 shows the pore volume results for fresh catalyst systems ZPGM-1 through ZPGM-5;
  • FIG. 5 shows the pore volume results for aged catalyst systems ZPGM-1 through ZPGM-5;
  • FIG. 6 shows the surface area summary for fresh and aged catalyst systems ZPGM-1 through ZPGM-5;
  • FIG. 7 shows the x-ray diffraction analysis of a ZPGM-1 catalyst system (fresh and aged Ce 0.6 La 0.4 Mn 0.6 Cu 0.4 O x powders);
  • FIG. 8 shows the x-ray diffraction analysis of a ZPGM-2 catalyst system (fresh and aged);
  • FIG. 9 shows the x-ray diffraction analysis of a ZPGM-3 catalyst system (fresh and aged).
  • FIG. 10 shows the x-ray diffraction analysis of a ZPGM-4 catalyst system (fresh and aged);
  • FIG. 11 shows the x-ray diffraction analysis of a ZPGM-5 catalyst system (fresh and aged);
  • FIG. 12 shows the x-ray diffraction analysis of a ZPGM-6 catalyst system (fresh and aged);
  • FIG. 13 shows the sweep test results for a ZPGM-1 catalyst system (fresh and aged).
  • FIG. 14 shows the sweep test results for a ZPGM-2 catalyst system (fresh and aged).
  • FIG. 15 shows the sweep test results for a ZPGM-3 catalyst system (fresh and aged).
  • FIG. 16 shows the sweep test results for a ZPGM-4 catalyst system (fresh and aged).
  • FIG. 17 shows the sweep test results for a ZPGM-5 catalyst system (fresh and aged).
  • FIG. 18 shows the sweep test results for a ZPGM-6 catalyst system (fresh and aged).
  • FIG. 19 shows the results of light off tests for an example of a Type D ZPGM transition metal catalyst
  • FIG. 20 shows the results of light off tests for an example of a Type D/Type H ZPGM transition metal catalyst
  • FIG. 21 shows the results of light off tests for an example of a Type D/Type H ZPGM transition metal catalyst
  • FIG. 22 shows the results of light off tests for an example of a Type F mixed metal oxide catalyst
  • FIG. 23 shows the results of light off tests for an example of a Type F mixed metal oxide catalyst
  • FIG. 24 shows the results of light off tests for an example of a Type F mixed metal oxide catalyst
  • FIG. 25 shows the results of light off tests for an example of a Type G ZPGM transition metal catalyst
  • FIG. 26 shows the results of light off tests for an example of a Type G ZPGM transition metal catalyst
  • FIG. 27 shows the results of light off tests for an example of a Type G/Type D ZPGM transition metal catalyst
  • FIG. 28 shows the results of light off tests for an example of a Type G/Type D ZPGM transition metal catalyst
  • FIG. 29 shows the results of ramp light off tests for an example of a Type D ZPGM transition metal catalyst
  • FIG. 30 shows the results of ramp light off tests for an example of a Type I
  • FIG. 31 shows light off test results for architecture 3.
  • FIG. 32 shows the results of a light-off test for a ZPGM-1 catalyst system (fresh and aged);
  • FIG. 33 shows the results of a light-off test for a ZPGM-2 catalyst system (fresh and aged);
  • FIG. 34 shows the results of a light-off test for a ZPGM-3 catalyst system (fresh and aged);
  • FIG. 35 shows the results of a light-off test for a ZPGM-4 catalyst system (fresh and aged);
  • FIG. 36 shows the results of a light-off test for a ZPGM-5 catalyst system (fresh and aged).
  • FIG. 37 shows the results of a light-off test for a ZPGM-6 catalyst system (fresh and aged).
  • catalyst system is defined in this specification to mean a substrate, a washcoat, and optionally an overcoat as illustrated by Architecture 1, Architecture 2, or Architecture 3 as set forth in FIG. 1 , 2 , and 3 , respectively.
  • substrate is defined in this specification to mean any material known in the art for supporting a catalyst and can be of any shape or configuration that yields a sufficient surface area for the deposit of the washcoat and/or overcoat, including, but not limited to a honeycomb, pellets, or beads.
  • washcoat is defined in this specification to mean a coating comprising one or more oxide solids that is coupled with a substrate.
  • overcoat is defined in this specification to mean a coating comprising one or more oxide solids that is coupled with a substrate and a washcoat.
  • oxide solid is defined in this specification to mean one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof.
  • carrier material oxide is defined in this specification to mean materials used for providing a surface for at least one catalyst and comprises one or more selected from the group consisting of oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovksite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium oxide, tin oxide, silicon dioxide, zeolite, and mixtures thereof.
  • oxygen storage material is defined in this specification to mean materials that can take up oxygen from oxygen-rich feed streams and release oxygen to oxygen-deficient feed streams.
  • the oxygen storage material comprises one or more oxides selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.
  • catalyst is defined in this specification to mean a catalyst for decreasing the amount of nitrogen oxide, hydrocarbon, carbon monoxide, and/or sulfur that is free of platinum group metals, preferably completely free of platinum group metals.
  • ZPGM Transition Metal Catalyst is defined in this specification to mean a catalyst comprising one or more transition metals.
  • Mated Metal Oxide Catalyst is defined in this specification to mean a catalyst comprising at least one transition metal and at least one other metal.
  • Zerolite Catalyst is defined in this specification to mean a catalyst comprising at least one zeolite and at least one transition metal.
  • transition metal is defined in this specification to mean the transition metals of the periodic table excluding the platinum group metals, which are scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, gold, mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, meitnerium, ununnilium, unununium, ununbium, and gallium.
  • platinum group metals which are scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, silver, cadmium, hafnium, tantalum, tungs
  • copper is defined in this specification to mean copper, copper complexes, copper atoms, or any other copper compounds known in the art.
  • impregnation component is defined in this specification to mean one or more components added to a washcoat and/or overcoat to yield a washcoat and/or overcoat comprising a catalyst.
  • the impregnation component comprises one or more selected from the group consisting of a transition metal, alkali and alkaline earth metal, cerium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof.
  • deposit is defined in this specification to include, without limitation, placing, adhering, curing, coating (such as vacuum coating), spraying, dipping, painting and any known process for coating a film on a substrate.
  • treating is defined in this specification to include, without limitation, precipitation, drying, firing, heating, evaporating, calcining, or mixtures thereof.
  • platinum group metals is defined in this specification to mean platinum, palladium, ruthenium, iridium, osmium, and rhodium.
  • Coupled with is defined in this specification to mean the washcoat and/or overcoat is in a relationship with the substrate or each other, such that they may be directly in contact with each other; or they may be associated with each other, but there may be something in between each of them, e.g. the overcoat may be coupled with a substrate, but a washcoat may be in between the substrate and the overcoat.
  • ZPGM Zero-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma-proliferative gamma, a number, e.g. “ZPGM-1”.
  • Type a letter, e.g. “Type A”.
  • the catalyst system of the present invention is free of platinum group metals; decreases the amount of at least one of carbon monoxide, nitrogen oxides, hydrocarbon, and sulfur emissions; and comprises one or more catalysts.
  • the substrate of the present invention may be, without limitation, a refractive material, a ceramic substrate, a honeycomb structure, a metallic substrate, a ceramic foam, a metallic foam, a reticulated foam, or suitable combinations, where the substrate has a plurality of channels and at least the required porosity. Porosity is substrate dependent as is known in the art. Additionally, the number of channels may vary depending upon the substrate used as is known in the art. The channels found in a monolith substrate are described in more detail below. The type and shape of a suitable substrate would be apparent to one of ordinary skill in the art. Preferably, all of the substrates, either metallic or ceramic, offer a three-dimensional support structure.
  • the substrate may be in the form of beads or pellets.
  • the beads or pellets may be formed from, without limitation, alumina, silica alumina, silica, titania, mixtures thereof, or any suitable material.
  • the substrate may be, without limitation, a honeycomb substrate.
  • the honeycomb substrate may be a ceramic honeycomb substrate or a metal honeycomb substrate.
  • the ceramic honeycomb substrate may be formed from, for example without limitation, sillimanite, zirconia, petalite, spodumene (lithium aluminum silicate), magnesium silicates, mullite, alumina, cordierite (e.g. Mg 2 A 14 Si 5 O 18 ), other alumino-silicate materials, silicon carbide, aluminum nitride, or combinations thereof.
  • Other ceramic substrates would be apparent to one of ordinary skill in the art.
  • the metal may be, without limitation, a heat-resistant base metal alloy, particularly an alloy in which iron is a substantial or major component.
  • the surface of the metal substrate may be oxidized at elevated temperatures above about 1000° C. to improve the corrosion resistance of the alloy by forming an oxide layer on the surface of the alloy. This oxide layer on the surface of the alloy may also enhance the adherence of a washcoat to the surface of the monolith substrate.
  • the substrate may be a monolithic carrier having a plurality of fine, parallel flow passages extending through the monolith.
  • the passages can be of any suitable cross-sectional shape and/or size.
  • the passages may be, for example without limitation, trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, or circular, although other shapes are also suitable.
  • the monolith may contain from about 9 to about 1200 or more gas inlet openings or passages per square inch of cross section, although fewer passages may be used.
  • the substrate can also be any suitable filter for particulates.
  • suitable forms of substrates may include, without limitation, woven filters, particularly woven ceramic fiber filters, wire meshes, disk filters, ceramic honeycomb monoliths, ceramic or metallic foams, wall flow filters, and other suitable filters.
  • Wall flow filters are similar to honeycomb substrates for automobile exhaust gas catalysts. They may differ from the honeycomb substrate that may be used to form normal automobile exhaust gas catalysts in that the channels of the wall flow filter may be alternately plugged at an inlet and an outlet so that the exhaust gas is forced to flow through the porous walls of the wall flow filter while traveling from the inlet to the outlet of the wall flow filter.
  • the catalyst of the present invention may be placed on the substrate in the form of a washcoat.
  • the oxide solids in the washcoat may be one or more carrier material oxide, one or more catalyst, or a mixture of carrier material oxide(s) and catalyst(s).
  • Carrier material oxides are normally stable at high temperatures (>1000° C.) and under a range of reducing and oxidizing conditions.
  • a preferable oxygen storage material is a mixture of ceria and zirconia; more preferably a mixture of (1) ceria, zirconia, and lanthanum or (2) ceria, zirconia, neodymium, and praseodymium.
  • a catalyst of the present invention comprises at least one oxygen storage material
  • the catalyst may comprise about 10 to about 90 weight percent oxygen storage material, preferably about 20 to about 80 weight percent, more preferably about 40 to about 75 weight percent.
  • the weight percent of the oxygen storage material is on the basis of the oxides.
  • washcoats of the present invention may be coupled with a substrate, preferably an amount that covers most of, or all of, the surface area of a substrate. In an embodiment, about 80 g/L to about 250 g/L of a washcoat may be coupled with a substrate.
  • a washcoat may be formed on the substrate by suspending the oxide solids in water to form an aqueous slurry and depositing the aqueous slurry on the substrate as a washcoat.
  • ком ⁇ онент may optionally be added to the aqueous slurry.
  • Other components such as acid or base solutions or various salts or organic compounds may be added to the aqueous slurry to adjust the rheology of the slurry and/or enhance binding of the washcoat to the substrate.
  • Some examples of compounds that can be used to adjust the rheology include, but are not limited to, ammonium hydroxide, aluminum hydroxide, acetic acid, citric acid, tetraethylammonium hydroxide, other tetralkylammonium salts, ammonium acetate, ammonium citrate, glycerol, commercial polymers such as polyethylene glycol, polyvinyl alcohol and other suitable polymers.
  • the slurry may be placed on the substrate in any suitable manner.
  • the substrate may be dipped into the slurry, or the slurry may be sprayed on the substrate.
  • Other methods of depositing the slurry onto the substrate known to those skilled in the art may be used in alternative embodiments.
  • the washcoat may be formed on the walls of the passages. Gas flowing through the flow passages can contact the washcoat on the walls of the passages as well as materials that are supported on the washcoat.
  • the oxygen storage material may improve the rheology of the washcoat slurry. Such an improvement may be seen in process control and/or manufacture of the catalyst system.
  • the enhanced rheology of the washcoat slurry that may be due to the presence of the oxygen storage material may enhance the adhesion of the washcoat slurry to the substrate.
  • a catalyst system may have one of the following three architectures.
  • a catalyst system may comprise a substrate ( 1 ) and a washcoat ( 2 ), wherein the washcoat comprises at least one catalyst. See FIG. 1 (Architecture 1).
  • a catalyst system may comprise a substrate ( 1 ), a washcoat ( 2 ), and an overcoat ( 3 ), wherein the washcoat ( 2 ) and overcoat ( 3 ) each comprise at least one catalyst. See FIG. 2 (Architecture 2).
  • a catalyst system may comprise a substrate ( 1 ), a washcoat ( 2 ), and an overcoat ( 3 ), wherein the overcoat ( 3 ) comprises at least one catalyst, but the washcoat ( 2 ) is free of catalyst, preferably completely free. See FIG. 3 (Architecture 3).
  • the washcoat ( 2 ) of the third catalyst system architecture comprises a carrier material oxide or mixtures thereof. Other components known to one of ordinary skill in the art may be included.
  • FIGS. 1-3 show how the layers are applied in order, but the end product may not have the layers as depicted due to, without limitation, the reactions that may occur between the layers.
  • the washcoat ( 2 ) may be deposited in three different ways. First, depositing all desired components in one step. Or second, depositing components without a catalyst, then separately depositing at least one impregnation component and heating (this separate deposit is also referred to as an impregnation step).
  • the impregnation component comprises, without limitation, transition metals, alkali and alkaline earth metals, cerium, lanthanum, yttrium, lanthanides, actinides, or mixtures thereof.
  • the impregnation step converts metal salts into metal oxides creating a washcoat ( 2 ) comprising a catalyst.
  • the overcoat ( 3 ) is typically applied after treating the washcoat ( 2 ), but treating is not required prior to application of the overcoat ( 3 ) in every embodiment.
  • the overcoat ( 3 ) is applied after the washcoat ( 2 ).
  • a catalyst system comprises a substrate ( 1 ) and one or more catalyst selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, and a zeolite catalyst.
  • a catalyst system of the present invention comprises a ZPGM transition metal catalyst.
  • a ZPGM transition metal catalyst comprises one or more transition metals.
  • the transition metal is copper, nickel, iron, manganese, silver, cobalt, tungsten, niobium, molybdenum, or chromium; more preferably copper, nickel, iron, or manganese; most preferably copper, nickel, or cobalt.
  • the ZPGM transition metal catalyst optionally comprises one or more of a carrier material oxide.
  • the catalyst comprises a perovskite, a spinel, a lyonsite, an oxygen storage material, alumina, or mixtures thereof; more preferably a spinel, an oxygen storage material, alumina, or mixtures thereof; most preferably at least one spinel and at least one oxygen storage material, or alumina and at least one oxygen storage material.
  • a catalyst of the present invention comprises at least one oxygen storage material
  • the catalyst may comprise about 10 to about 90 weight percent oxygen storage material, preferably about 20 to about 80 weight percent, more preferably about 40 to about 75 weight percent.
  • the weight percent of the oxygen storage material is on the basis of the oxides.
  • the catalysts may optionally further comprise one or more of a transition metal, alkaline earth metal, ceria, and mixtures thereof.
  • the transition metal is iron, manganese, or mixtures thereof.
  • the alkaline earth metal is magnesium, barium, or mixtures thereof.
  • the catalyst comprises at least one transition metal and at least one carrier material oxide.
  • the transition metals may be a single transition metal, or a mixture of transition metals which includes, but is not limited to, chromium, manganese, iron, cobalt, nickel, copper, silver, niobium, molybdenum, and tungsten.
  • the preferred transition metals are copper, nickel and cobalt.
  • the total amount of the transition metal(s) are present in about 5% to about 50% by weight of the total catalyst weight and may be present in any ratio of transitional metals.
  • the catalyst referred to as “Type D”, comprises copper and one or more carrier material oxides.
  • additional transition metals may be included.
  • the copper may be applied through impregnation as discussed herein.
  • the copper in the catalyst may be present in about 5% to about 50% by weight, preferably about 5% to about 30%, more preferably about 15% by weight.
  • a catalyst system referred to as “ZPGM-6”, comprises a substrate, a washcoat, and an overcoat.
  • the substrate comprises cordierite.
  • the washcoat comprises a spinel and at least one oxygen storage material, preferably the oxygen storage material is a mixture of cerium, zirconium, and lanthanum.
  • the spinel in this embodiment comprises magnesium aluminum oxides. Additionally, the oxygen storage material and the spinel may be present in the washcoat in a ratio of 40 to about 60 by weight. If an impregnation step is required, copper, cerium, zirconium, and lanthanum may be added and heated to convert metal salts into metal oxides that create a washcoat comprising the catalyst.
  • the overcoat comprises copper oxide, a spinel, and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the spinel in this embodiment comprises magnesium aluminum oxides.
  • the spinel and oxygen storage material of the overcoat may be present in the overcoat in a ratio of about 60 to about 40.
  • the copper in the overcoat is present in about 5% to about 50%, preferably about 10% to about 16% by weight.
  • a catalyst system referred to as “ZPGM-5”, comprises a substrate, a washcoat, and an overcoat.
  • the substrate comprises cordierite.
  • the washcoat comprises lanthanum-doped aluminum oxide and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium. Additionally, the oxygen storage material and the lanthanum-doped aluminum oxide may be present in the washcoat in a ratio of about 40 to about 60.
  • the optional impregnation components comprise copper, cerium, zirconium, and lanthanum.
  • the overcoat comprises copper oxide, lanthanum-stabilized aluminum oxide, and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the aluminum oxide and oxygen storage material of the overcoat may be present in the overcoat in a ratio of about 75 to about 25.
  • the copper in the overcoat is present in about 5% to about 50%, preferably about 15% by weight.
  • a catalyst system referred to as “ZPGM-4”, comprises a substrate, a washcoat, and an overcoat.
  • the washcoat comprises tin aluminum oxide and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the tin aluminum oxide and the oxygen storage material may be present in the washcoat in a ratio of from about 25:75 to about 75:25, preferably in a ratio of about 60 to about 40.
  • the optional impregnation components comprise copper, cerium, zirconium, and lanthanum.
  • the overcoat comprises aluminum, copper, and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, and lanthanum.
  • the aluminum oxide and oxygen storage material may be present in the overcoat in a ratio of about 60 to about 40. According to an embodiment, there is about 5% to about 30% copper by weight in the overcoat, preferably about 10% to about 20%, more preferably about 12%.
  • a catalyst system referred to as “ZPGM-3”, comprises a substrate and a washcoat.
  • the washcoat comprises copper, tin aluminum oxide, and at least one oxygen storage material, preferably the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium.
  • the tin aluminum oxide and the oxygen storage material may be present in the washcoat in a ratio of about 60 to about 40.
  • the impregnation components comprise copper, cerium, zirconium, and lanthanum.
  • the cerium, zirconium, and lanthanum may be present in the washcoat in a ratio of about 60 to about 30 to about 10.
  • the washcoat may comprise additional transition metals. According to an embodiment, there is about 5% to about 30% copper by weight in the washcoat, preferably about 10% to about 20%, more preferably about 12%.
  • a catalyst system referred to as “ZPGM-2”, comprises a substrate and a washcoat.
  • the washcoat may comprise, without limitation, copper, aluminum oxide, and at least one oxygen storage material, preferably the oxygen storage material is a mixture of cerium, zirconium, and lanthanum.
  • the aluminum oxide and the oxygen storage material may be present in the washcoat in a ratio of about 60 to about 40.
  • the copper in the washcoat may be about 5% to about 20% copper by weight, preferably about 8%.
  • the washcoat coat may optionally comprise additional transitional metals and/or ceria.
  • a catalyst system referred to as “ZPGM-1”, comprises a substrate and a washcoat.
  • the washcoat comprises at least one carrier material oxide and a perovskite; preferably the carrier material oxide comprises an oxygen storage material, more preferably comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, praseodymium, and mixtures thereof, and the perovskite preferably is a mixture of cerium, lanthanum, manganese and copper, having the specific formula Ce 0.6 La 0.4 Mn 0.6 Cu 0.4 O 3 .
  • the catalyst comprises at least one transition metal, at least one alkaline earth metal, cerium, and at least one carrier material oxide.
  • the transition metal, alkaline earth metal and cerium are present in about 5% to about 50% by weight in any ratio of the three components.
  • the alkaline earth metals comprise one or more selected from the group consisting of magnesium, calcium, barium, and strontium.
  • the transition metals may be a single transition metal, or a mixture of transition metals which include, but is not limited to, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, and tungsten.
  • the catalyst comprises at least one transition metal, at least one alkaline earth metal, and at least one carrier material oxide.
  • the transition metal may be a single transition metal, or a mixture of transition metals which include, but is not limited to, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and silver.
  • the alkaline earth metal may be, but is not limited to, magnesium, calcium, barium or strontium.
  • the preferred transition metals are copper, nickel, and cobalt, while the preferred alkaline earth metals are barium and strontium.
  • the alkaline earth metal and the transition metal may be present in a molar ratio of about 1:10 to 1:1 and at about 2% to about 50% weight of the catalyst.
  • the catalyst comprises at least one transition metal and a perovskite having the formula ABO 3 .
  • the transition metal may be, but is not limited to, copper, nickel, cobalt, manganese, iron, chromium, niobium, molybdenum, tungsten, and silver.
  • the transition metals are copper, nickel, and/or cobalt.
  • “A” comprises lanthanum, cerium, magnesium, calcium, barium, strontium, lanthanides, actinides, or a mixture thereof.
  • “B” comprises iron, manganese, copper, nickel, cobalt, cerium, or mixtures thereof.
  • the transition metal(s) is present in about 2% to about 30% by weight.
  • the Type E catalyst comprises a perovskite (ABO 3 ), at least one transition metal, and at least one a carrier material oxide.
  • the transition metal may be a single transition metal, or a mixture of transition metals which includes, but is not limited to, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, or mixtures thereof.
  • the perovskite and transition metal are present in about 5% to about 50% by weight.
  • the catalyst comprises at least one transition metal and a spinel having the formula AB 2 O 4 .
  • the transition metal may be, but is not limited to, copper, nickel, cobalt, manganese, iron, chromium, niobium, molybdenum, tungsten, and silver.
  • the preferred transition metals include, copper, nickel, and cobalt; more preferably copper.
  • “A” and “B” each comprise aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, niobium, titanium, tin, or mixtures thereof.
  • a preferred spinel is MgAl 2 O 4 .
  • the transition metal(s) are present in about 2% to about 30% by weight.
  • the Type G catalyst comprises a spinel (AB 2 O 4 ), a transition metal, and a carrier material oxide.
  • the transition metal may be a single transition metal, or a mixture of transition metals which includes, but is not limited to, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and/or silver.
  • a preferred spinel is MgAl 2 O 4 .
  • the spinel and transition metal(s) are present in about 5% to about 50% by weight.
  • a catalyst may be a mixed metal oxide catalyst, which comprises at least one transition metal and at least one other metal.
  • the other metals of the mixed metal oxide may include, but are not limited to alkali and alkaline earth metal, lanthanides, or actinides.
  • the mixed metal oxide may be a spinel, a perovskite, a delafossite, a lyonsite, a garnet, or a pyrochlore.
  • the catalyst referred to as “Type B”
  • Type B comprises a perovskite having the formula ABO 3 or a related structure with the general formula A a-x B x MO b , wherein “a” is 1 or 2, “b” is 3 when “a” is 1 or “b” is 4 when “a” is 2, and “z” is a number defined by 0.1 ⁇ x ⁇ 0.7.
  • A comprises lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, or mixtures thereof.
  • B comprises a single transition metal, or a mixture of transition metals including but not limited to iron, manganese, copper, nickel, cobalt, and cerium, or mixture thereof.
  • the catalyst may have the formula AMn 1-x Cu x O 3 , wherein “A” is lanthanum, cerium, barium, strontium, a lanthanide, or an actinide and “x” is 0 to 1.
  • the Type B catalyst may have the formula ACe 1-x Cu x O 3 , wherein “A” is barium, strontium, or calcium, and “x” is 0 to 1. According to an embodiment, about 10 g/L to about 180 g/L of the formula ABO 3 may be coupled with the substrate.
  • the Type B catalyst comprises a perovskite (ABO 3 ) or related structure (with general formula A a-x B x MO b ) and one or more of a carrier material oxide.
  • the perovskite or related structure is present in about 5% to about 50% by weight.
  • the catalyst referred to as “Type F”, comprises a spinel having the formula AB 2 O 4 .
  • “A” and “B” of the formula is aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, titanium, tin, or mixtures thereof.
  • the Type F catalyst comprises a spinel and a carrier material oxide.
  • the spinel is present in about 5% to about 50% by weight.
  • a catalyst may be a zeolite catalyst comprising a zeolite or mixture of zeolites and at least one transition metal.
  • a zeolite is mixed aluminosillicates with regular interconnected pores.
  • the zeolite includes, but is not limited to ZSM5, heulandite, chabazite, or mixtures thereof, preferably ZSM5.
  • the catalyst referred to as “Type I” comprises at least one transition metal impregnated into a zeolite or mixtures of zeolite.
  • the transition metal(s) may be a single transition metal or a mixture of transition metal which includes, but is not limited to, chromium, gallium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and silver.
  • the transition metals are selected from the group consisting of copper, nickel, gallium, cobalt, and mixtures thereof.
  • the transition metals may be present in about 3% to about 25% by weight in any ratio of transition metals.
  • the catalysts of the present invention may reduce pollutants emitted from exhaust. This is done by passing exhaust substantially through a catalyst system, such that the flowing exhaust reduces the pollutants.
  • the exhaust includes, but is not limited to exhaust from an automobile, vehicle, factory, train, airplane, building, and laboratory.
  • Pollutants are any compounds, substances, gases, or waste that causes damage to water, air, land, and any other part of the environment, including carbon monoxide, hydrocarbons, nitrogen oxides, and sulfur.
  • the catalysts of the present invention to decrease the amount of nitrogen oxide emissions. For example: NO+1/2O 2 ⁇ NO 2 and 6NO 2 +8NH 3 ⁇ 7N 2 +12H 2 O.
  • the catalyst also decreases the amount of the unburned hydrocarbons and carbon monoxide by oxidizing them. For example: 2C x H y +(2x+y/2)O 2 ⁇ 2xCO 2 +yH 2 O or 2CO+O 2 ⁇ 2CO 2 .
  • the catalysts may also decrease the amount of sulfur emissions.
  • a catalyst system comprises a first catalyst system and a second catalyst system.
  • the first catalyst system may be any catalyst described herein.
  • the second catalyst system comprises a catalyst comprising at least one platinum group metal, wherein the catalyst may comprise any platinum group metal known in the art, including, but not limited to mixtures of platinum group metals and carrier material oxides.
  • the first catalyst system and the second catalyst system may be in an orientation such that a gas stream is capable of passing through the first catalyst system followed by the second catalyst system in series or vice versa.
  • a catalyst system may comprise more than a first and a second catalyst system, e.g. a third catalyst system.
  • a washcoat having the properties discussed herein may be prepared by methods well known in the art.
  • the washcoat may comprise any of the catalysts and/or additional components described herein.
  • the washcoat is deposited on a substrate and is treated.
  • the treating is done at a temperature between 300° C. and 700° C., preferably about 550° C.
  • the treating may last from about 2 to about 6 hours, preferably about 4 hours.
  • the washcoat is impregnated with at least one impregnation component.
  • the impregnation component includes, without limitation, a transition-metal salt or salts being dissolved in water and impregnated on the washcoat.
  • the washcoat with the impregnation components are treated.
  • the treating may be performed at about 300° C. to about 700° C., preferably about 550° C.
  • the treating may last from about 2 to about 6 hours, preferably about 4 hours.
  • the substrate, the washcoat, and the impregnation components may be treated to form the catalyst composition before or after the washcoat and/or the impregnation components are added to the substrate.
  • the washcoat and the impregnation component may be treated before coating.
  • the impregnation method may be performed on an overcoat. After depositing the overcoat, the overcoat is impregnated with at least one impregnation component.
  • the impregnation component includes, without limitation, a transition-metal salt or salts being dissolved in water and impregnated on the overcoat.
  • the overcoat with the impregnation components are treated.
  • the treating may be performed at about 300° C. to about 700° C., preferably about 550° C.
  • the treating may last from about 2 hours to about 6 hours, preferably about 4 hours.
  • the method of precipitation includes precipitating a transition metal salt or salts on a washcoat.
  • the transition metal salt or salts may be precipitated with, but is not limited to NH 4 OH, (NH 4 ) 2 CO 3 , tetraethylammonium hydroxide, other tetralkylammonium salts, ammonium acetate, or ammonium citrate.
  • the washcoat may be any washcoat described herein.
  • the precipitated transition metal salt or salts and washcoat are treated. The treating may be from about 2 hours to about 24 hours.
  • the precipitated transition metal salt or salts and the washcoat are deposited on a substrate followed by treating for about 2 hours to about 6 hours, preferably about 4 hours at a temperature of about 300° C.
  • an overcoat may be deposited on the treated precipitated transition metal salt or salts and washcoat and treated again.
  • the overcoat may be treated for about 2 hours to about 6 hours, preferably about 4 hours and at a temperature of about 300° C. to about 700° C., preferably about 550° C.
  • a catalyst and a carrier material oxide are milled together.
  • the catalyst can be synthesized by any chemical technique such as, but not limited to solid-state synthesis, precipitation, or any other technique known in the art.
  • the milled catalyst and carrier material oxide are deposited on a substrate in the form of a washcoat and then treated.
  • the treatment may be from about 2 hours to about 6 hours, preferably about 4 hours and at a temperature of about 300° C. to about 700° C., preferably about 550° C.
  • an overcoat may be deposited on the treated catalyst after cooling to about room temperature.
  • the overcoat, washcoat and substrate are treated for about 2 hours to about 6 hours, preferably about 4 hours and at a temperature of 300° C. to about 700° C., preferably about 550° C.
  • FIG. 4 shows the measured pore volume for the fresh catalyst systems ZPGM-1 through ZPGM-5 and FIG. 5 shows the measured pore volume for the aged catalyst systems ZPGM-1 through ZPGM-5.
  • the aged catalyst systems were aged at 950° C. for 16 hours with 10% H 2 O and air.
  • the y-axis on the right side of FIG. 4 is for the pore volume (cm 3 /g) of ZPGM-1 only.
  • the pore volumes were measured using a Micromeritics® (Norcross, Ga.) TriStar 3000 gas adsorption analyzer at 77K.
  • the pore volumes were obtained from the nitrogen adsorption isotherms using the Barrett-Joiner-Halenda (BJH) method (E. P. Barrett, L. G. Joyner, P. P. Halenda, “The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms,” J. Am. Chem. Soc. (1951), 73, 373-380).
  • BJH Barrett-Joiner-Halenda
  • the results in FIGS. 4 and 5 show that the pore volume decreases for all the catalyst systems (ZPGM-1 through ZPGM-5) upon aging.
  • the average pore volume for the fresh ZPGM-1 decreases from 0.106 cm 3 /g to 0.017 cm 3 /g for the aged catalyst.
  • the average pore volume for the fresh ZPGM-2 decreases from 0.173 cm 3 /g to 0.116 cm 3 /g for the aged catalyst.
  • the average pore volume for the fresh ZPGM-3 decreases from 0.107 cm 3 /g to 0.010 cm 3 /g for the aged catalyst.
  • the average pore volume for the fresh ZPGM-4 decreases from 0.190 cm 3 /g to 0.142 cm 3 /g for the aged catalyst.
  • the average pore volume for the fresh ZPGM-5 decreases from 0.213 cm 3 /g to 0.122 cm 3 /g for the aged catalyst.
  • the surface areas for the fresh and aged ZPGM catalyst systems are presented in FIG. 6 .
  • the aged catalyst systems were aged at 950° C. for 16 hours with 10% H 2 O and air.
  • the surface areas were measured using a Micromeritics® (Norcross, Ga.) TriStar 3000 gas adsorption analyzer at 77K.
  • the surface areas were calculated using the BET (Brunauer, Emmitt and Teller) method (S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309).
  • the results in FIG. 6 show that the surface area decreases for all catalyst systems (ZPGM-1 through ZPGM-5) upon aging.
  • the surface area decreases from 18.72 m 2 /g for the fresh ZPGM-1 to 2.76 m 2 /g for the aged catalyst.
  • the surface area decreases from 38.60 m 2 /g for the fresh ZPGM-2 to 15.48 m 2 /g for the aged catalyst.
  • the surface area decreases from 30.78 m 2 /g for the fresh ZPGM-3 to 16.71 m 2 /g for the aged catalyst.
  • the surface area decreases from 46.95 m 2 /g for the fresh ZPGM-4 to 22.06 m 2 /g for the aged catalyst.
  • the surface area decreases from 53.45 m 2 /g for the fresh ZPGM-5 to 24.02 m 2 /g for the aged catalyst.
  • FIGS. 7-12 show the X-ray diffraction (XRD) patterns of fresh and aged catalyst systems ZPGM-1 through ZPGM-6; the aged catalyst systems were aged at 950° C. for 16 hrs with 10% H 2 O and air.
  • XRD X-ray diffraction
  • the XRD analysis was conducted to determine the crystalline phases present for each catalyst system.
  • the XRD patterns were measured on a Rigaku® powder diffractometer (MiniFlexTM) using Cu Ka radiation in the 2-theta range of 20-70° with a step size of 0.05° and a dwell time of 2 s.
  • the tube voltage and current were set at 40 kV and 30 mA, respectively.
  • the resulting diffraction patterns were analyzed using the International Centre for Diffraction Data (ICDD) database.
  • ICDD International Centre for Diffraction Data
  • FIG. 7 shows the XRD spectra of the fresh and aged ZPGM-1 catalyst system, Ce 0.6 La 0.4 Mn 0.6 Cu 0.4 O 3 , shows the presence of the perovskite (open circles) and fluorite (filled squares) structures. The fluorite and the perovskite structures are larger in the aged sample as evidenced by the sharper peaks.
  • FIG. 8 shows the XRD patterns of fresh and aged ZPGM-2 catalyst system, 8% Cu impregnated on Al 2 O 3 +Ce 0.64 Zr 0.21 La 0.15 O 2 (60:40 weight ratio of Al 2 O 3 to Ce 0.64 Zr 0.21 La 0.15 O 2 ) (160 g/ml).
  • the XRD spectrum of the fresh ZPGM-2 catalyst system shows the presence of the fluorite structure (open squares), alumina (A) and CuO (filled circles).
  • the aged ZPGM-2 catalyst system shows fluorite (open squares), CuAl 2 O 4 (filled diamonds) and alumina (A). The fluorite structure is larger in the aged sample as evidenced by the sharper peaks.
  • FIG. 9 shows the XRD patterns of fresh and aged ZPGM-3 catalyst system, 8% Cu+6.1% Ce+2.4% Zr+1.5% La impregnated on 15% Sn—Al 2 O 3 +Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 (60:40 weight ratio of Sn—Al 2 O 3 to Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ) (200 g/L).
  • the XRD of the fresh ZPGM-3 catalyst system shows the presence of the fluorite structure (open circles), ZrO 2 (open squares), alumina (A) and CuO (filled circles).
  • the aged ZPGM-3 catalyst system shows fluorite (open circles), ZrO 2 (open squares), SnO 2 (filled circles), CuAl 2 O 4 (filled diamonds) and alumina (A).
  • the cordierite peak in the aged sample is from the substrate.
  • the tin oxide dissociates from the alumina, the Cu reacts with the Al 2 O 3 to form CuAl 2 O 4 .
  • FIG. 10 shows the XRD patterns of fresh and aged ZPGM-4 catalyst system, which is composed of an overcoat containing 12% Cu impregnated on Ce 0.6 Zr 0.21 La 0.15 O 2 +Al 2 O 3 (60:40 weight ratio of Ce 0.6 Zr 0.21 La 0.15 O 2 to Al 2 O 3 ) and a washcoat containing 8% Cu+6.1% Ce+2.4% Zr+1.5% La impregnated impregnated on 15% Sn—Al 2 O 3 +Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 (60:40 weight ratio of Sn—Al 2 O 3 to Ce 0.6 Zr 0.3 Nd 0.05 O 2 ).
  • the XRD spectrum of the fresh ZPGM-4 catalyst system shows the presence of the fluorite structure (filled circles), CeO 2 (open squares), alumina (A) and CuO (filled squares).
  • the aged ZPGM-4 catalyst system shows fluorite (filled circles), CeO 2 (open squares), SnO 2 (open circles), CuAl 2 O 4 (filled diamonds) and alumina (A).
  • the tin oxide dissociates from the alumina, the Cu reacts with the Al 2 O 3 to form CuAl 2 O 4 .
  • FIG. 11 shows the XRD patterns of fresh and aged ZPGM-5 catalyst system, which is composed of an overcoat containing 12.4% CuO impregnated on La—Al 2 O 3 +Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 (25:75 weight ratio of La—Al 2 O 3 to Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ) (65 g/L) and a washcoat containing 8% Cu+6.1% Ce+2.4% Zr+1.5% La impregnated on La—Al 2 O 3 +Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 (60:40 weight ratio of La—Al 2 O 3 to Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ) (180 g/L).
  • the XRD spectrum of the fresh ZPGM-5 catalyst system shows the presence of the fluorite structure (filled circles) and alumina (A).
  • the aged ZPGM-5 catalyst system shows fluorite (filled circles), CuAl 2 O 4 (filled diamonds) and alumina (A). During the aging the Cu reacts with the Al 2 O 3 to form CuAl 2 O 4 .
  • FIG. 12 shows the XRD patterns of fresh and aged ZPGM-6 catalyst system, which is composed of an overcoat containing 10% Cu+12% Ce impregnated on MgAl 2 O 4 +16% Cu impregnated on Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 (60:40 weight ratio of Ce impregnated on MgAl 2 O 4 to 16% Cu impregnated on Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ) (65 g/L) and a washcoat containing 4% Cu+6.1% Ce+2.4% Zr+1.5% La impregnated on MgAl 2 O 4 +Ce 0.64 Zr 0.21 La 0.15 O 2 (60:40 weight ratio of MgAl 2 O 4 to Ce 0.64 Zr 0.21 La 0.15 O 2 ) (180 g/L).
  • the XRD spectrum of the fresh ZPGM-6 catalyst system shows the presence of two fluorite structures (filled and open circles), and MgAl 2 O 4 (open diamonds).
  • the aged ZPGM-6 catalyst system shows two fluorite structures (filled and open circles), MgAl 2 O 4 (open diamonds), CuAl 2 O 4 (filled diamonds), and CuO (filled squares).
  • CZL and CuO became more crystalline, and some CuAl 2 O 4 formed.
  • FIGS. 13-18 show the sweep test results for catalyst systems ZPGM-1 through ZPGM-6 (as described above in Examples 3-8), respectively.
  • the sweep test was performed with an inlet temperature of 600° C., an air/fuel span of ⁇ 0.2 and a cycle frequency of 1 Hz.
  • a sweep test indicates the catalyst performance at various R-values (moles of reductant divided by moles of oxidant). High conversions over a large range of R-values indicate a promising catalyst because it can perform well under rich (R-values>1) and lean (R-values ⁇ 1) engine conditions.
  • the aged catalyst systems were aged at 1050° C. for 10 hrs cycling between a 56 second rich segment and a 4 second lean segment.
  • FIG. 13 shows the sweep test results for the fresh and aged ZPGM-1 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>1.05, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with R-value>0.85.
  • the CO conversion of the aged ZPGM-1 decreases with increasing R-value.
  • the HC conversion for the aged ZPGM-1 is best for R-values between 0.95 and 1.05.
  • FIG. 14 shows the sweep test results for the fresh and aged ZPGM-2 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>1.05, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with R-value>0.85.
  • the catalytic properties for CO, hydrocarbons and NO decrease after aging.
  • the CO and HC conversions of the aged ZPGM-2 decrease with increasing R-value.
  • FIG. 15 shows the sweep test results for the fresh and aged ZPGM-3 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>1.05, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with increasing R-values.
  • the catalytic properties for CO, hydrocarbons and NO decrease after aging.
  • the CO and HC conversions of the aged ZPGM-3 decrease with increasing R-value.
  • the NO conversion for the aged ZPGM-3 increases with R-values>0.95.
  • FIG. 16 shows the sweep test results for the fresh and aged ZPGM-4 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>0.975, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with increasing R-values.
  • the catalytic properties for CO, hydrocarbons and NO decrease after aging.
  • the CO and HC conversions of the aged ZPGM-4 decrease with increasing R-value.
  • the NO conversion for the aged ZPGM-4 increases with R-values>0.95.
  • FIG. 17 shows the sweep test results for the fresh and aged ZPGM-5 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>0.975, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with increasing R-values.
  • the catalytic properties for CO, hydrocarbons and NO decrease after aging.
  • the CO and HC conversions of the aged ZPGM-5 decrease with increasing R-value.
  • the NO conversion for the aged ZPGM-5 increases with R-values>1.05.
  • FIG. 18 shows the sweep test results for the fresh and aged ZPGM-6 catalyst system.
  • the sweep results for the fresh catalyst show that the CO conversion decreases with R-values>0.975, while the hydrocarbon (HC) conversion decreases with increasing R-values.
  • the NO conversion increases with increasing R-values.
  • the catalytic properties for CO, hydrocarbons and NO decrease after aging.
  • the CO and HC conversions of the aged ZPGM-6 decrease with increasing R-value.
  • the NO conversion for the aged ZPGM-6 increases with R-values>0.975.
  • FIGS. 19-21 show the light-off test results for examples of Type D or Type H ZPGM Transition Metal Catalysts. It should be noted that a catalyst may fall into one or more types, such as here, where the catalyst is both Type D and Type H.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • FIG. 19 shows the results for Type D/H catalyst with a composition of 16% Cu/Ce 0.3 Zr 0.6 Nd 0.05 Pr 0.05 O 2 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type D and Type H.
  • the maximum conversion for NO is about 2% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 20 shows the results for Type D/H catalyst with a composition of 12% Cu/Ce 0.6 Zr 0.3 La 0.1 O 2 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type D and Type H.
  • the maximum conversion for NO is about 4% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 21 shows the results for Type D/H catalyst with a composition of 10% Cu+12% Ce/La—Al 2 O 3 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type D and Type H.
  • the maximum conversion for NO is about 3% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIGS. 22-24 show the light-off test results for examples of Type F catalyst.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • FIG. 22 shows the results for Type F catalyst with a composition of CuLa 0.04 Al 1.96 O 4 .
  • the maximum conversions for NO and HC at 640° C. are about 6% and 38%, respectively.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 23 shows the results for Type F catalyst with a composition of Cu 0.5 Fe 0.5 La 0.04 Al 1.96 O 4 .
  • the maximum NO conversion is about 1% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 24 shows the results for Type F catalyst with a composition of CuLa 0.04 Al 1.47 Mn 0.49 O 4 .
  • the maximum conversions for NO and HC at 640° C. are about 2% and 27%, respectively. Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIGS. 25 -28 show the light-off test results for examples of Type G/Type D catalyst. It should be noted that a catalyst may fall into one or more types, such as here, where the catalyst is both Type G and Type D.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • FIG. 25 shows the results for Type G/Type D catalyst with a composition of 10% Ag/Cu 0.5 Fe 0.5 La 0.04 Al 1.96 O 4 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type G and Type D.
  • the maximum conversions for NO and HC at 640° C. are about 1% and 33%, respectively. Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 26 shows the results for Type G/Type D catalyst with a composition of 10% Cu/CuLa 0.04 Al 1.96 O 4 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type G and Type D.
  • FIG. 27 shows the results for Type G/Type D catalyst with a composition of 20% CuO/MgLa 0.04 Al 1.96 O 4 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type G and Type D.
  • FIG. 28 shows the results for Type G/Type D catalyst with a composition of 10% Cu+12% Ce/MgLa 0.04 Al 1.96 O 4 .
  • a catalyst may fall into one or more types, such as here, where the catalyst is both Type G and Type D.
  • the maximum NO conversion is about 2% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the CO and HC performance deteriorates.
  • FIG. 29 shows the light-off test results for an example of Type D catalyst.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • FIG. 29 shows the results for Type D catalyst with a composition of 12% CuO/(Ce 0.6 Zr 0.3 La 0.1 O 2 +MgLa 0.04 Al 1.96 O 4 (40:60)).
  • FIG. 30 shows the light-off test results for an example of Type I Zeolite catalyst.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • FIG. 30 shows the results for Type I catalyst with a composition of 5% Ga+8% Cu/(ZSM-5).
  • FIG. 31 shows the light-off test results for an example of Architecture Type 3 Catalyst, which comprises a substrate, a washcoat, and an overcoat, wherein the overcoat comprises at least one catalyst, but the washcoat does not (washcoat comprises La—Al 2 O 3 +Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ; 60:40; 100 g/L and overcoat comprises 12% Cu on Ce 0.6 Zr 0.3 Nd 0.05 Pr 0.05 O 2 ; 150 g/L).
  • a light-off test was performed on aged (800° C. for 16 hours, composed of a 56 second rich segment and a 4 second lean segment) catalysts of the present invention. The test was performed by increasing the temperature from about 100° C. to 640° C.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • the maximum NO conversion is about 6% at 640° C.
  • Increasing the R-value to 1.5 improves the NO conversion, but the HC performance deteriorates.
  • FIGS. 32-37 show the light-off test results for ZPGM-1 through ZPGM-6.
  • the light-off test measures the conversions of nitrogen oxide, carbon monoxide, and hydrocarbons as a function of the catalyst system temperature. For a specific temperature, a higher conversion signifies a more efficient catalyst. Conversely, for a specific conversion, a lower temperature signifies a more efficient catalyst.
  • the light-off test for the fresh catalyst system shows that the CO and HC exhibit T 50 s at 288° C. and at 503° C., respectively.
  • the maximum NO conversion is about 19% at 600° C.
  • the aged catalyst shows a T 50 for CO at about 600° C.
  • the maximum conversions for HC and NO are 19% and 2%, respectively, at 600° C.
  • the light-off test for the fresh catalyst system shows that the CO and HC exhibit T 50 s at 205° C. and at 389° C., respectively.
  • the maximum NO conversion is about 22% at 600° C.
  • the catalyst performance decreases for CO, HC and NO.
  • the maximum conversions for CO, HC and NO are 27%, 24% and 3%, respectively, at 600° C.
  • the light-off test for the fresh catalyst system shows that the CO, HC and NO exhibit T 50 s at 205° C., at 389° C., and 651° C., respectively.
  • the catalyst performance decreases for CO, HC and NO.
  • the aged catalyst shows a T 50 for CO and HC at about 599° C. and 651° C., respectively.
  • the maximum conversion for NO is 5% at 700° C.
  • the light-off test for the fresh catalyst system shows that the CO, HC and NO exhibit T 50 s at 254° C., at 442° C., and 636° C., respectively.
  • the catalyst performance decreases for CO, HC and NO.
  • the aged catalyst shows a T 50 for CO and HC at about 462° C. and 604° C., respectively.
  • the maximum conversion for NO is about 30% at 770° C.
  • the light-off test for the fresh catalyst system shows that the CO, HC and NO exhibit T 50 s at 262° C., at 449° C., and 608° C., respectively.
  • the catalyst performance decreases for CO, HC and NO.
  • the aged catalyst shows a T 50 for CO and HC at about 571° C. and 654° C., respectively.
  • the maximum conversion for NO is about 1% at 700° C.
  • the light-off test for the fresh catalyst system shows that the CO, HC and NO exhibit T 50 s at 262° C., at 463° C., and 622° C., respectively.
  • the catalyst performance decreases for CO, HC and NO.
  • the aged catalyst shows a T 50 for CO and HC at about 425° C. and 613° C., respectively.
  • the maximum conversion for NO is about 23% at 730° C.

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US8685352B2 (en) 2014-04-01
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AU2009263035A1 (en) 2009-12-30
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