GB2553339A

GB2553339A - Improved NOx trap

Info

Publication number: GB2553339A
Application number: GB1614923.9A
Authority: GB
Inventors: Richard Chandler Guy; Richard Phillips Paul; David Reid Stuart; Strehlau Wolfgang; Swallow Daniel
Original assignee: Johnson Matthey PLC
Current assignee: Johnson Matthey PLC
Priority date: 2016-09-02
Filing date: 2016-09-02
Publication date: 2018-03-07
Also published as: GB201614923D0; DE102017120207A1; RU2019109451A3; CN109690041B; KR20190043165A; US20190176129A1; EP3910171A1; KR102445791B1; CN109690041A; BR112019003380A2; JP2022169500A; GB201714011D0; US10213768B2; EP3507469A1; US10532344B2; WO2018042181A1; RU2744310C2; RU2019109451A; JP2019531883A; GB2556153A

Abstract

A nitrogen oxides (NOx) trap comprising a noble metal, a NOx storage component, a support, and a ceria-containing material; the ceria-containing material has a surface area of less than 80 m2/g. Alternatively, the ceria-containing material is pre-aged prior to incorporation into the NOx trap composition. The disclosure also includes a NOx trap catalyst comprising the NOx trap composition, exhaust systems comprising the NOx trap catalyst, and a method for treating exhaust gas utilizing the NOx trap catalyst. The noble metal may be a palladium group metal (PGM). The storage component may comprise barium and the support may comprise magnesia-alumina. The NOx trap may have a lower oxygen storage capacity compared to a fresh NOx trap that has not been pre-aged. The trap may be supported on a metal or ceramic substrate which may be a filter or flow-through monolith. The trap may treat an exhaust gas of a diesel engine.

Description

(54) Title of the Invention: Improved NOx trap

Abstract Title: NOx trap with pre-aged ceria material (57) A nitrogen oxides (NO_X) trap comprising a noble metal, a NO_X storage component, a support, and a ceria-containing material; the ceria-containing material has a surface area of less than 80 m²/g. Alternatively, the ceria-containing material is pre-aged prior to incorporation into the NO_X trap composition. The disclosure also includes a NO_X trap catalyst comprising the NO_X trap composition, exhaust systems comprising the NO_X trap catalyst, and a method for treating exhaust gas utilizing the NO_X trap catalyst. The noble metal may be a palladium group metal (PGM). The storage component may comprise barium and the support may comprise magnesia-alumina. The NO_X trap may have a lower oxygen storage capacity compared to a fresh NO_X trap that has not been pre-aged. The trap may be supported on a metal or ceramic substrate which may be a filter or flow-through monolith. The trap may treat an exhaust gas of a diesel engine.

Intellectual

Property

Office

Application No. GB1614923.9

RTM

Date :24 February 2017

The following terms are registered trade marks and should be read as such wherever they occur in this document:

Micromeritics

Tristar

SCRF

Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo

IMPROVED ΝΟχ TRAP

FIELD OFTHE INVENTION

The invention relates to a NO_X trap for exhaust systems for internal combustion engines, and a method for treating an exhaust gas from an internal combustion engine.

BACKGROUND OF THE INVENTION

Internal combustion engines produce exhaust gases containing a variety of pollutants, including hydrocarbons, carbon monoxide, nitrogen oxides (“NO_X“), sulfur oxides, and particulate matter. Increasingly stringent national and regional legislation has lowered the amount of pollutants that can be emitted from such diesel or gasoline engines. Many different techniques have been applied to exhaust systems to clean the exhaust gas before it passes to atmosphere.

One such technique utilized to clean exhaust gas is the NO_X adsorber catalyst (or “NO_X trap”). NO_X traps are devices that adsorb NO_X under lean exhaust conditions, release the adsorbed NO_X under rich conditions, and reduce the released NO_X to form N₂. A NO_X trap typically includes a NO_X adsorbent for the storage of NO_xand an oxidation/reduction catalyst.

The NO_X adsorbent component is typically an alkaline earth metal (such as Ba, Ca, Sr, and Mg), an alkali metal (such as K, Na, Li, and Cs), a rare earth metal (such as La, Y, Pr, and Nd), or combinations thereof. These metals are typically found in the form of oxides. The oxidation/reduction catalyst is typically one or more noble metals, preferably platinum, palladium, and/or rhodium. Typically, platinum is included to perform the oxidation function and rhodium is included to perform the reduction function. The oxidation/reduction catalyst and the NO_X adsorbent are typically loaded on a support material such as an inorganic oxide for use in the exhaust system.

The NO_X trap performs three functions. First, nitric oxide reacts with oxygen to produce NO₂ in the presence of the oxidation catalyst. Second, the

N0₂ is adsorbed by the NO_X adsorbent in the form of an inorganic nitrate (for example, BaO or BaCC>3 is converted to Ba(NC>3)2 on the NO_X adsorbent). Lastly, when the engine runs under rich conditions, the stored inorganic nitrates decompose to form NO or NO₂ which are then reduced to form N₂ by reaction with carbon monoxide, hydrogen and/or hydrocarbons in the presence of the reduction catalyst. Typically, the nitrogen oxides are converted to nitrogen, carbon dioxide and water in the presence of heat, carbon monoxide and hydrocarbons in the exhaust stream.

During NO_X trap regeneration, reductant from the engine is consumed in 10 reducing stored NO_X and stored O₂ in the catalyst. The level of oxygen storage capacity (OSC) is much greater in a fresh NO_X trap compared to an aged NO_X trap, resulting in the need for much longer regeneration lengths for fresh traps.

As with any automotive system and process, it is desirable to attain still further improvements in exhaust gas treatment systems. We have discovered a new NO_X trap that shows a significant reduction in OSC, but with the same NO_Xactivity when tested on an engine.

SUMMARY OF THE INVENTION

In a first aspect of the invention there is provided a NO_X trap composition 20 comprising a noble metal, a NO_X storage component, a support, and a ceriacontaining material, wherein the ceria-containing material has a surface area of less than 80 m²/g.

In a second aspect of the invention there is provided a NO_X trap composition comprising a noble metal, a NO_X storage component, a support, and a ceria-containing material, wherein the ceria-containing material is pre-aged prior to incorporation into the NO_xtrap.

In a third aspect of the invention there is provided a NO_X trap catalyst comprising the NO_X trap composition as hereinbefore defined supported on a metal or ceramic substrate.

In a fourth aspect of the invention there is provided a NO_X trap catalyst comprising the NO_X trap composition as hereinbefore defined, wherein the composition is extruded to form a flow-through or filter substrate.

In a fifth aspect of the invention there is provided an emission treatment system for treating a flow of a combustion exhaust gas comprising the NO_X trap catalyst as hereinbefore defined.

In a sixth aspect of the invention there is provided a method of treating an exhaust gas from an internal combustion engine comprising contacting the exhaust gas with the NO_xtrap catalyst as hereinbefore defined.

In a seventh aspect of the invention there is provided a method of reducing the oxygen storage capacity of a ceria-containing material in a NO_xtrap composition, comprising pre-aging the ceria-containing material prior to incorporating it into the NO_xtrap composition.

In an eighth aspect of the invention there is provided the use of a pre-aged ceria-containing material to reduce the oxygen storage capacity of a NO_X trap composition.

DEFINITIONS

The term “washcoat” is well known in the art and refers to an adherent coating that is applied to a substrate, usually during production of a catalyst.

The acronym “PGM” as used herein refers to “platinum group metal”. The term “platinum group metal” generally refers to a metal selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt, preferably a metal selected from the group consisting of Ru, Rh, Pd, Ir and Pt. In general, the term “PGM” preferably refers to a metal selected from the group consisting of Rh, Pt and Pd.

The term “mixed oxide” as used herein generally refers to a mixture of oxides in a single phase, as is conventionally known in the art. The term “composite oxide” as used herein generally refers to a composition of oxides having more than one phase, as is conventionally known in the art.

DETAILED DESCRIPTION OF THE INVENTION

The NOxtrap composition of the invention comprises a noble metal, a NO_Xstorage component, a support, and a ceria-containing material, wherein the ceria-containing material has a surface area of less than 80 m²/g. Preferably, the ceria-containing material has a surface area of 40-75 m²/g.

In a further aspect of the invention, the NO_X trap composition of the invention comprises a noble metal, a NO_X storage component, a support, and a ceria-containing material, wherein the ceria-containing material is pre-aged prior to incorporation into the NO_xtrap composition.

The noble metal is preferably platinum, palladium, gold, rhodium, or mixtures thereof; most preferably, the noble metal is platinum, palladium, or mixtures thereof, i.e. a mixture of platinum and palladium. Preferably, the noble metal loading in the NO_X trap composition will range from 40 to 250 g/ft³. The NO_xtrap composition preferably comprises 0.1 to 10 weight percent noble metal, more preferably 0.5 to 5 weight percent noble metal, and most preferably 1 to 3 weight percent noble metal.

The support is preferably an inorganic oxide, and more preferably includes oxides of Groups 2, 3, 4, 5, 13 and 14 elements. Most preferably, the support is an alumina, silica, titania, zirconia, magnesia, niobia, tantalum oxide, molybdenum oxide, tungsten oxide, a mixed oxide or composite oxide of any two or more thereof (e.g. silica-alumina, magnesia-alumina, ceria-zirconia or aluminaceria-zirconia), and mixtures thereof. Especially preferred is a magnesia-alumina support. The magnesia-alumina is preferably a spinel, a magnesia-alumina mixed metal oxide, a hydrotalcite or hydrotalcite-like material, and combinations of two or more thereof. More preferably, the magnesia-alumina support is a spinel.

Preferred support materials preferably have surface areas in the range 10 to 1500 m²/g, pore volumes in the range 0.1 to 4 mL/g, and pore diameters from about 10 to 1000 Angstroms. High surface area supports having a surface area greater than 80 m²/g are particularly preferred, e.g. high surface area ceria or alumina. Other preferred support materials include magnesia/alumina composite oxides, optionally further comprising a cerium-containing component, e.g. ceria.

In such cases the ceria may be present on the surface of the magnesia/alumina composite oxide, e.g. as a coating, or may be present as a dopant.

The NO_X storage component preferably comprises alkaline earth metals (such as barium, calcium, strontium, and magnesium), alkali metals (such as potassium, sodium, lithium, and cesium), rare earth metals (such as lanthanum, yttrium, praseodymium and neodymium), or combinations thereof. Most preferably, the NO_X storage component comprises barium. These metals are typically found in the form of oxides.

Preferably, the NO_X storage component is deposited on the support (such as a magnesia-alumina). The NO_X storage component may be loaded onto the support by any known means, the manner of addition is not considered to be particularly critical. For example, a barium compound (such as barium acetate) may be added to a magnesia-alumina by impregnation, adsorption, ionexchange, incipient wetness, precipitation, spray drying, or the like. Preferably, if the NO_X storage component is deposited on the support, the support contains at least 0.5 weight percent NO_X storage component.

The ceria-containing material is preferably ceria, ceria-zirconia, ceriazirconia-alumina, or mixtures thereof. More preferably, the ceria-containing material is ceria, and in particular, particulate ceria. The ceria-containing material has a surface area of less than 80 m²/g, more preferably less than 75 m²/g. The ceria-containing material may have a surface area of 40 to 75 m²/g, preferably 50 to 70 m²/g. The ceria-containing material may be manufactured in such a way to produce a surface area of less than 80 m²/g or may be a higher surface area ceria-containing material that has been treated (such as by pre-aging) to produce a surface area of less than 80 m²/g.

Pre-aging the ceria-containing material prior to incorporation into the NO_Xtrap composition will preferably reduce the oxygen storage capacity of the NO_Xtrap composition by greater than 40% compared to a fresh NO_xtrap composition that contains ceria-containing material that was not pre-aged.

The NO_X trap composition of the invention may comprise further components that are known to the skilled person. For example, the compositions of the invention may further comprise at least one binder and/or at least one surfactant. Where a binder is present, dispersible alumina binders are preferred.

The NO_X trap composition of the present invention may be prepared by any suitable means. Preferably, the one or more noble metals, and/or ceriacontaining material, and/or NO_X storage material are loaded onto the support by any known means to form the NO_X trap catalyst composition. The manner of addition is not considered to be particularly critical. For example, a noble metal compound (such as platinum nitrate) and a cerium compound (such as cerium nitrate, as a precursor to the ceria-containing material) may be supported on a support (such as an alumina) by impregnation, adsorption, ion-exchange, incipient wetness, precipitation, or the like, or by any other means commonly known in the art.

The order of addition of the noble metal compound and/or NO_X storage component and/or ceria-containing material to the support is not considered critical. For example, the platinum, NO_X storage component and ceria-containing material may be added to the support simultaneously, or may be added sequentially in any order.

In some embodiments of the invention, the ceria-containing material is pre-aged prior to incorporation into the NO_X trap composition. The pre-aging is preferably performed by heating the ceria-containing material at a temperature greater than 700 °C (more preferably, greater than 750 °C, and most preferably at least 800 °C; for example, between 750 and 950 °C) in the absence of added water. By added water, it is meant that water is not deliberately added to the heating process. The heating may be performed in an oxygen-containing gas (such as air) or in an inert gas (such as nitrogen). The heating is preferably performed for greater than 0.25 hours, more preferably greater than 0.5 hour, and most preferably at least 1 hour. Following pre-aging, the surface area of the ceria-containing material is preferably less than 80 m²/g. Surface area is measured using a Micromeritics Tristar 3000 system, running a 30 point analysis. The samples are degassed prior to analysis at 350 °C for 1 hour and the surface area measured using nitrogen at target relative pressures from ~2 to 100 kPa.

A further aspect of the invention is a NO_X trap catalyst comprising the NO_Xtrap composition as hereinbefore described supported on a metal or ceramic substrate. The substrate may be a flow-through substrate or a filter substrate, but is preferably a flow-through monolith substrate.

The flow-through monolith substrate has a first face and a second face defining a longitudinal direction therebetween. The flow-through monolith substrate has a plurality of channels extending between the first face and the second face. The plurality of channels extend in the longitudinal direction and provide a plurality of inner surfaces (e.g. the surfaces of the walls defining each channel). Each of the plurality of channels has an opening at the first face and an opening at the second face. For the avoidance of doubt, the flow-through monolith substrate is not a wall flow filter.

The first face is typically at an inlet end of the substrate and the second face is at an outlet end of the substrate.

The channels may be of a constant width and each plurality of channels may have a uniform channel width.

Preferably within a plane orthogonal to the longitudinal direction, the monolith substrate has from 100 to 500 channels per square inch, preferably from 200 to 400. For example, on the first face, the density of open first channels and closed second channels is from 200 to 400 channels per square inch. The channels can have cross sections that are rectangular, square, circular, oval, triangular, hexagonal, or other polygonal shapes.

The monolith substrate acts as a support for holding catalytic material. Suitable materials for forming the monolith substrate include ceramic-like materials such as cordierite, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica magnesia or zirconium silicate, or of porous, refractory metal. Such materials and their use in the manufacture of porous monolith substrates is well known in the art.

It should be noted that the flow-through monolith substrate described herein is a single component (i.e. a single brick). Nonetheless, when forming an emission treatment system, the monolith used may be formed by adhering together a plurality of channels or by adhering together a plurality of smaller monoliths as described herein. Such techniques are well known in the art, as well as suitable casings and configurations of the emission treatment system.

In an alternative embodiment of the invention, the NO_X trap catalyst comprising the NO_X trap composition as hereinbefore described is extruded to form a flow-through or filter substrate.

In embodiments wherein the NO_X trap catalyst comprises a ceramic substrate, the ceramic substrate may be made of any suitable refractory material,

e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates and metallo aluminosilicates (such as cordierite and spodumene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred.

In embodiments wherein the NO_X trap catalyst comprises a metallic substrate, the metallic substrate may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminium in addition to other trace metals.

Preferably, the NO_xtrap catalyst as hereinbefore described is prepared by depositing the NO_X trap composition as hereinbefore described on the substrate using washcoat procedures. A representative process for preparing the NO_xtrap catalyst using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention.

The washcoating is preferably performed by first slurrying finely divided particles of the NO_X trap composition in an appropriate solvent, preferably water, to form a slurry. The slurry preferably contains between 5 to 70 weight percent solids, more preferably between 10 to 50 weight percent. Preferably, the particles are milled or subject to another comminution process in order to ensure that substantially all of the solid particles have a particle size of less than 20 microns in an average diameter, prior to forming the slurry. Additional components, such as stabilizers or promoters, may also be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes.

The substrate may then be coated one or more times with the slurry such that there will be deposited on the substrate the desired loading of the NO_X trap composition.

Preferably, the NO_X trap catalyst comprises a substrate and at least one layer on the substrate. In one embodiment, the at least one layer comprises the NO_X trap composition as hereinbefore described. This can be produced by the washcoat procedure described above. One or more additional layers may be added to the one layer of NO_xtrap composition.

In embodiments wherein one or more additional layers are present (i.e. in addition to the NO_X trap composition), the one or more additional layers have a different composition to the first layer comprising the NO_xtrap composition.

The one or more additional layers may comprise one zone or a plurality of zones, e.g. two or more zones. Where the one or more additional layers comprise a plurality of zones, the zones are preferably longitudinal zones. The plurality of zones, or each individual zone, may also be present as a gradient, i.e. a zone may not be of a uniform thickness along its entire length, to form a gradient. Alternatively a zone may be of uniform thickness along its entire length.

In some preferred embodiments, one additional layer, i.e. a second layer, is present.

Typically, the second layer comprises a platinum group metal (PGM) (referred to below as the “second platinum group metal”). It is generally preferred that the second layer comprises the second platinum group metal (PGM) as the only platinum group metal (i.e. there are no other PGM components present in the catalytic material, except for those specified).

The second PGM may be selected from the group consisting of platinum, palladium, and a combination or mixture of platinum (Pt) and palladium (Pd). Preferably, the platinum group metal is selected from the group consisting of palladium (Pd) and a combination or a mixture of platinum (Pt) and palladium (Pd). More preferably, the platinum group metal is selected from the group consisting of a combination or a mixture of platinum (Pt) and palladium (Pd).

It is generally preferred that the second layer is (i.e. is formulated) for the oxidation of carbon monoxide (CO) and/or hydrocarbons (HCs).

Preferably, the second layer comprises palladium (Pd) and optionally platinum (Pt) in a ratio by weight of 1:0 (e.g. Pd only) to 1:4 (this is equivalent to a ratio by weight of Pt:Pd of 4:1 to 0:1). More preferably, the second layer comprises platinum (Pt) and palladium (Pd) in a ratio by weight of < 4:1, such as <3.5:1.

When the platinum group metal is a combination or mixture of platinum and palladium, then the second layer comprises platinum (Pt) and palladium (Pd) in a ratio by weight of 5:1 to 3.5:1, preferably 2.5:1 to 1:2.5, more preferably 1:1 to 2:1.

The second layer typically further comprises a support material (referred to herein below as the “second support material”). The second PGM is generally disposed or supported on the second support material.

The second support material is preferably a refractory oxide. It is preferred that the refractory oxide is selected from the group consisting of alumina, silica, ceria, silica alumina, ceria-alumina, ceria-zirconia and alumina-magnesium oxide. More preferably, the refractory oxide is selected from the group consisting of alumina, ceria, silica-alumina and ceria-zirconia. Even more preferably, the refractory oxide is alumina or silica-alumina, particularly silica-alumina.

A particularly preferred second layer comprises a silica-alumina support, platinum, palladium, barium, a molecular sieve, and a platinum group metal (PGM) on an alumina support, e.g. a rare earth-stabilised alumina. Particularly preferably, this preferred second layer comprises a first zone comprising a silicaalumina support, platinum, palladium, barium, a molecular sieve, and a second zone comprising a platinum group metal (PGM) on an alumina support, e.g. a rare earth-stabilised alumina. This preferred second layer may have activity as an oxidation catalyst, e.g. as a diesel oxidation catalyst (DOC).

A further preferred second layer comprises, consists of, or consists essentially of a platinum group metal on alumina. This preferred second layer may have activity as an oxidation catalyst, e.g. as a NO₂-maker catalyst.

A further preferred second layer comprises a platinum group metal, rhodium, and a cerium-containing component.

A particularly preferred second layer comprises rhodium, a ceriumcontaining component, and an inorganic support. Preferably the inorganic support comprises alumina, e.g is alumina. In preferred embodiments comprising this preferred second layer, the cerium-containing component in the preferred second layer is not pre-aged prior to incorporation into the layer, and does not have a surface area of less than 80 m²/g. In other words, in preferred embodiments comprising this preferred second layer, the ceria-containing component in the first layer is a different material to the ceria-containing component in the first layer. For example, the surface area of the ceriacontaining component in the first layer is lower than the surface area of the ceriacontaining component in the second layer.

A particularly preferred embodiment of the NO_xtrap catalyst of the present invention therefore comprises a first layer comprising a ceria-containing component having a surface area of less than 80 m²/g, e.g. 40-75 m²/g, preferably 55-70 m²/g; a Ba/Ce/magnesium-aluminate spinel; platinum; palladium; and alumina; and a second layer comprising a ceria-containing component having a higher surface area than the ceria-containing component present in the first layer; rhodium; and alumina.

In other preferred embodiments, more than one of the preferred second layers described above are present, in addition to the NO_X trap composition. In such embodiments, the one or more additional layers may be present in any configuration, including zoned configurations.

The NO_X trap composition may be disposed or supported on the second layer or the substrate (e.g. the plurality of inner surfaces of the through-flow monolith substrate), preferably the second layer is disposed or supported on the NO_xtrap composition.

The second layer may be disposed or supported on the substrate (e.g. the plurality of inner surfaces of the through-flow monolith substrate).

The second layer may be disposed or supported on the entire length of the substrate or the NO_xtrap composition. Alternatively the second layer may be disposed or supported on a portion, e.g. 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%, of the substrate or the NO_xtrap composition.

Preferably, the entire length of the substrate is coated with the NO_X trap composition.

The NO_X trap catalyst of the present invention may be prepared by processes well known in the prior art. Preferably, the NO_X trap is prepared by depositing the NO_X trap composition on the substrate using washcoat procedures. Preferably, the entire length of the substrate is coated with the NO_Xtrap composition so that a washcoat of the NO_X trap composition covers the entire surface of the substrate.

A representative process for preparing the NO_X trap catalyst using a washcoat procedure is set forth below. It will be understood that the process below can be varied according to different embodiments of the invention.

The NO_X trap is preferably prepared using a washcoat procedure. The noble metal and NO_X storage component are preferably added to the support and then combined with the ceria-containing material prior to the washcoating step. The noble metal and NO_X storage component may be loaded onto the support by any known means, the manner of addition is not considered to be particularly critical. For example, a platinum or palladium compound (such as platinum nitrate) may be added to the support by impregnation, adsorption, ion-exchange, incipient wetness, spray drying, precipitation, or the like to produce a supported noble metal, followed by addition of a NO_X storage component (such as barium acetate).

A further aspect of the invention is an emission treatment system for treating a flow of a combustion exhaust gas that comprises the NO_xtrap catalyst as hereinbefore described. In preferred systems, the internal combustion engine is a diesel engine, preferably a light duty diesel engine. The NO_X trap catalyst may be placed in a close-coupled position or in the underfloor position.

The emission treatment system typically further comprises an emissions control device.

The emissions control devices is preferably downstream of the NO_X trap catalyst.

Examples of an emissions control device include a diesel particulate filter (DPF), a lean NO_X trap (LNT), a lean NO_X catalyst (LNC), a selective catalytic reduction (SCR) catalyst, a diesel oxidation catalyst (DOC), a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, an ammonia slip catalyst (ASC) and combinations of two or more thereof. Such emissions control devices are all well known in the art.

Some of the aforementioned emissions control devices have filtering substrates. An emissions control device having a filtering substrate may be selected from the group consisting of a diesel particulate filter (DPF), a catalysed soot filter (CSF), and a selective catalytic reduction filter (SCRF™) catalyst.

It is preferred that the emission treatment system comprises an emissions control device selected from the group consisting of a lean NO_X trap (LNT), an ammonia slip catalyst (ASC), a diesel particulate filter (DPF), a selective catalytic reduction (SCR) catalyst, a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, and combinations of two or more thereof. More preferably, the emissions control device is selected from the group consisting of a diesel particulate filter (DPF), a selective catalytic reduction (SCR) catalyst, a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, and combinations of two or more thereof. Even more preferably, the emissions control device is a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF™) catalyst.

When the emission treatment system of the invention comprises an SCR catalyst or an SCRF™ catalyst, then the emission treatment system may further comprise an injector for injecting a nitrogenous reductant, such as ammonia, or an ammonia precursor, such as urea or ammonium formate, preferably urea, into exhaust gas downstream of the NO_X trap catalyst and upstream of the SCR catalyst or the SCRF™ catalyst.

Such an injector may be fluidly linked to a source (e.g. a tank) of a nitrogenous reductant precursor. Valve-controlled dosing of the precursor into the exhaust gas may be regulated by suitably programmed engine management means and closed loop or open loop feedback provided by sensors monitoring the composition of the exhaust gas.

Ammonia can also be generated by heating ammonium carbamate (a solid) and the ammonia generated can be injected into the exhaust gas.

Alternatively or in addition to the injector, ammonia can be generated in situ (e.g. during rich regeneration of a LNT disposed upstream of the SCR catalyst or the SCRF™ catalyst), e.g. a NO_xtrap catalyst comprising the NO_xtrap composition of the invention. Thus, the emission treatment system may further comprise an engine management means for enriching the exhaust gas with hydrocarbons.

The SCR catalyst or the SCRF™ catalyst may comprise a metal selected from the group consisting of at least one of Cu, Hf, La, Au, In, V, lanthanides and Group VIII transition metals (e.g. Fe), wherein the metal is supported on a refractory oxide or molecular sieve. The metal is preferably selected from Ce, Fe, Cu and combinations of any two or more thereof, more preferably the metal is Fe or Cu.

The refractory oxide for the SCR catalyst or the SCRF™ catalyst may be selected from the group consisting of AI₂O₃, TiO₂, CeO₂, SiO₂, ZrO₂ and mixed oxides containing two or more thereof. The non-zeolite catalyst can also include tungsten oxide (e.g. V₂O5/WO3/TiO₂, WOVCeZrO₂, WOx/ZrO₂ or Fe/WOVZrO₂).

It is particularly preferred when an SCR catalyst, an SCRF™ catalyst or a washcoat thereof comprises at least one molecular sieve, such as an aluminosilicate zeolite or a SAPO. The at least one molecular sieve can be a small, a medium or a large pore molecular sieve. By “small pore molecular sieve” herein we mean molecular sieves containing a maximum ring size of 8, such as CHA; by “medium pore molecular sieve” herein we mean a molecular sieve containing a maximum ring size of 10, such as ZSM-5; and by “large pore molecular sieve” herein we mean a molecular sieve having a maximum ring size of 12, such as beta. Small pore molecular sieves are potentially advantageous for use in SCR catalysts.

In the emission treatment system of the invention, preferred molecular sieves for an SCR catalyst or an SCRF™ catalyst are synthetic aluminosilicate zeolite molecular sieves selected from the group consisting of AEI, ZSM-5, ZSM20, ERI including ZSM-34, mordenite, ferrierite, BEA including Beta, Y, CHA, LEV including Nu-3, MCM-22 and EU-1, preferably AEI or CHA, and having a silica-to-alumina ratio of about 10 to about 50, such as about 15 to about 40.

In a first emission treatment system embodiment, the emission treatment system comprises the NO_X trap catalyst of the invention and a catalysed soot filter (CSF). The NO_xtrap catalyst is typically followed by (e.g. is upstream of) the catalysed soot filter (CSF). Thus, for example, an outlet of the NO_X trap catalyst is connected to an inlet of the catalysed soot filter.

A second emission treatment system embodiment relates to an emission treatment system comprising the NO_X trap catalyst of the invention, a catalysed soot filter (CSF) and a selective catalytic reduction (SCR) catalyst.

The NO_X trap catalyst is typically followed by (e.g. is upstream of) the catalysed soot filter (CSF). The catalysed soot filter is typically followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogenous reductant injector may be arranged between the catalysed soot filter (CSF) and the selective catalytic reduction (SCR) catalyst. Thus, the catalysed soot filter (CSF) may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst.

In a third emission treatment system embodiment, the emission treatment system comprises the NO_X trap catalyst of the invention, a selective catalytic reduction (SCR) catalyst and either a catalysed soot filter (CSF) or a diesel particulate filter (DPF).

In the third emission treatment system embodiment, the NO_X trap catalyst of the invention is typically followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogenous reductant injector may be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the catalyzed monolith substrate may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. The selective catalytic reduction (SCR) catalyst are followed by (e.g. are upstream of) the catalysed soot filter (CSF) or the diesel particulate filter (DPF).

A fourth emission treatment system embodiment comprises the NO_X trap catalyst of the invention and a selective catalytic reduction filter (SCRF™) catalyst. The NO_X trap catalyst of the invention is typically followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRF™) catalyst.

A nitrogenous reductant injector may be arranged between the NO_X trap catalyst and the selective catalytic reduction filter (SCRF™) catalyst. Thus, the NO_X trap catalyst may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRF™) catalyst.

When the emission treatment system comprises a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF™) catalyst, such as in the second to fourth exhaust system embodiments described hereinabove, an ASC can be disposed downstream from the SCR catalyst or the SCRF™ catalyst (i.e. as a separate monolith substrate), or more preferably a zone on a downstream or trailing end of the monolith substrate comprising the SCR catalyst can be used as a support for the ASC.

Another aspect of the invention relates to a vehicle. The vehicle comprises an internal combustion engine, preferably a diesel engine. The internal combustion engine, preferably the diesel engine, is coupled to an emission treatment system of the invention.

It is preferred that the diesel engine is configured or adapted to run on fuel, preferably diesel fuel, comprising < 50 ppm of sulfur, more preferably < 15 ppm of sulfur, such as < 10 ppm of sulfur, and even more preferably < 5 ppm of sulfur.

The vehicle may be a light-duty diesel vehicle (LDV), such as defined in US or European legislation. A light-duty diesel vehicle typically has a weight of < 2840 kg, more preferably a weight of < 2610 kg. In the US, a light-duty diesel vehicle (LDV) refers to a diesel vehicle having a gross weight of < 8,500 pounds (US lbs). In Europe, the term light-duty diesel vehicle (LDV) refers to (i) passenger vehicles comprising no more than eight seats in addition to the driver’s seat and having a maximum mass not exceeding 5 tonnes, and (ii) vehicles for the carriage of goods having a maximum mass not exceeding 12 tonnes.

Alternatively, the vehicle may be a heavy-duty diesel vehicle (HDV), such as a diesel vehicle having a gross weight of > 8,500 pounds (US lbs), as defined in US legislation.

A further aspect of the invention is a method of treating an exhaust gas from an internal combustion engine comprising contacting the exhaust gas with the NO_X trap catalyst as hereinbefore described. In preferred methods, the exhaust gas is a rich gas mixture. In further preferred methods, the exhaust gas cycles between a rich gas mixture and a lean gas mixture.

In some preferred methods of treating an exhaust gas from an internal combustion engine, the exhaust gas is at a temperature of about 180 to 300 °C.

In further preferred methods of treating an exhaust gas from an internal combustion engine, the exhaust gas is contacted with one or more further emissions control devices, in addition to the NO_X trap catalyst as hereinbefore described. The emissions control device or devices is preferably downstream of the NOxtrap catalyst.

Examples of a further emissions control device include a diesel particulate filter (DPF), a lean NO_X trap (LNT), a lean NO_X catalyst (LNC), a selective catalytic reduction (SCR) catalyst, a diesel oxidation catalyst (DOC), a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, an ammonia slip catalyst (ASC) and combinations of two or more thereof. Such emissions control devices are all well known in the art.

It is preferred that the method comprises contacting the exhaust gas with an emissions control device selected from the group consisting of a lean NO_Xtrap (LNT), an ammonia slip catalyst (ASC), a diesel particulate filter (DPF), a selective catalytic reduction (SCR) catalyst, a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, and combinations of two or more thereof. More preferably, the emissions control device is selected from the group consisting of a diesel particulate filter (DPF), a selective catalytic reduction (SCR) catalyst, a catalysed soot filter (CSF), a selective catalytic reduction filter (SCRF™) catalyst, and combinations of two or more thereof. Even more preferably, the emissions control device is a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF™) catalyst.

When the the method of the invention comprises contacting the exhaust gas with an SCR catalyst or an SCRF™ catalyst, then the method may further comprise the injection of a nitrogenous reductant, such as ammonia, or an ammonia precursor, such as urea or ammonium formate, preferably urea, into exhaust gas downstream of the NO_X trap catalyst and upstream of the SCR catalyst or the SCRF™ catalyst.

Such an injection may be carried out by an injector. The injector may be fluidly linked to a source (e.g. a tank) of a nitrogenous reductant precursor. Valve-controlled dosing of the precursor into the exhaust gas may be regulated by suitably programmed engine management means and closed loop or open loop feedback provided by sensors monitoring the composition of the exhaust gas.

Alternatively or in addition to the injector, ammonia can be generated in situ (e.g. during rich regeneration of a LNT disposed upstream of the SCR catalyst or the SCRF™ catalyst). Thus, the method may further comprise enriching of the exhaust gas with hydrocarbons.

The refractory oxide for the SCR catalyst or the SCRF™ catalyst may be selected from the group consisting of AI₂O₃, TiO₂, CeO₂, SiO₂, ZrO₂ and mixed oxides containing two or more thereof. The non-zeolite catalyst can also include tungsten oxide (e.g. ν₂Ο₅Λ/νθ₃/ΤίΟ₂, WOVCeZrO₂, WOx/ZrO₂ or Fe/WO7ZrO₂).

In the method of treating an exhaust gas of the invention, preferred molecular sieves for an SCR catalyst or an SCRF™ catalyst are synthetic aluminosilicate zeolite molecular sieves selected from the group consisting of AEI, ZSM-5, ZSM-20, ERI including ZSM-34, mordenite, ferrierite, BEA including Beta, Y, CHA, LEV including Nu-3, MCM-22 and EU-1, preferably AEI or CHA, and having a silica-to-alumina ratio of about 10 to about 50, such as about 15 to about 40.

In a first embodiment, the method comprises contacting the exhaust gas with the NO_X trap catalyst of the invention and a catalysed soot filter (CSF). The NOx trap is typically followed by (e.g. is upstream of) the catalysed soot filter (CSF). Thus, for example, an outlet of the NO_X trap catalyst is connected to an inlet of the catalysed soot filter.

A second embodiment of the method of treating an exhaust gas relates to a method comprising contacting the exhaust gas with the NO_xtrap catalyst of the invention, a catalysed soot filter (CSF) and a selective catalytic reduction (SCR) catalyst.

The NOxtrap catalyst trap is typically followed by (e.g. is upstream of) the catalysed soot filter (CSF). The catalysed soot filter is typically followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogenous reductant injector may be arranged between the catalysed soot filter (CSF) and the selective catalytic reduction (SCR) catalyst. Thus, the catalysed soot filter (CSF) may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst.

In a third embodiment of the method of treating an exhaust gas, the method comprises contacting the exhaust gas with the NO_X trap catalyst of the invention, a selective catalytic reduction (SCR) catalyst and either a catalysed soot filter (CSF) or a diesel particulate filter (DPF).

In the third embodiment of the method of treating an exhaust gas, the NO_Xtrap catalyst of the invention is typically followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. A nitrogenous reductant injector may be arranged between the oxidation catalyst and the selective catalytic reduction (SCR) catalyst. Thus, the NO_xtrap catalyst may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction (SCR) catalyst. The selective catalytic reduction (SCR) catalyst are followed by (e.g. are upstream of) the catalysed soot filter (CSF) or the diesel particulate filter (DPF).

A fourth embodiment of the method of treating an exhaust gas comprises the NO_X trap catalyst of the invention and a selective catalytic reduction filter (SCRF™) catalyst. The NO_xtrap catalyst of the invention is typically followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRF™) catalyst.

When the emission treatment system comprises a selective catalytic reduction (SCR) catalyst or a selective catalytic reduction filter (SCRF™) catalyst, such as in the second to fourth method embodiments described hereinabove, an ASC can be disposed downstream from the SCR catalyst or the SCRF™ catalyst (i.e. as a separate monolith substrate), or more preferably a zone on a downstream or trailing end of the monolith substrate comprising the SCR catalyst can be used as a support for the ASC.

A further aspect of the invention is a method of reducing the oxygen storage capacity of a ceria-containing material in a NO_X trap composition, comprising pre-aging the ceria-containing material prior to incorporating it into the NO_xtrap composition. Preferably the pre-aging is performed by heating the ceriacontaining material at a temperature greater than 700 °C, e.g. between 750 and 950 °C, in the absence of added water.

Without wishing to be bound by theory, it is proposed that by lowering the oxygen storage capacity of the ceria-containing material, a NO_X trap catalyst that contains this material will have better selectivity towards N₂ production when the NO_X is released and reduced during a rich purge, as there will be a higher amount of reductants available to the reduce the NO_X.

A further aspect of the invention is the use of a pre-aged ceria-containing material to reduce the oxygen storage capacity of a NO_X trap composition.

Preferably the ceria-containing material is pre-aged by heating the ceriacontaining material at a temperature greater than 700 °C, e.g. between 750 and 950 °C, in the absence of added water.

The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

EXAMPLE 1: PREPARATION OF NO_XTraps (LNTs)

LNT 1A : NO_xTrap with Pre-Aged Ceria

A 400 cell per square inch (cpsi) flow-through cordierite substrate monolith is coated with a NO_X trap catalyst formulation comprising two layers. The lower layer washcoat comprises Pt, Pd, 37% of a Ba/Ce/magnesium-aluminate spinel and 53% ceria (93% of the total ceria loading includes particulate ceria). The surface area of the ceria used is 70 m²/g, following pre-aging at 800 °C for 1 hour in air, and without any added water. The surface area of the particulate ceria was 120 m²/g prior to pre-aging. The washcoat is coated on the virgin substrate monolith using the method disclosed in WO 99/47260, followed by drying for 30 minutes in a forced air drier at 100 °C and then firing at 500 °C for 2 hours.

A second slurry is prepared consisting of slurried particulate ceria followed by the addition of appropriate amounts of a soluble rhodium salt. The pH is then increased to 7.5 with the addition of NH₃ to hydrolyse the Rh onto the ceria, followed by the addition of alumina binders. The second slurry is applied to the calcined lower layer from via the inlet and outlet channels. The part is then dried and calcined at 500 °C.

Comparative LNT 1B: NO_xTrap without Pre-aging Ceria

Comparative LNT 1B is prepared in exactly the same way as LNT 1A except the particulate ceria used in the lower layer washcoat is not subjected to pre-aging and has a surface area of >120 m²/g.

EXAMPLE 2: Oxygen Storage Testing

Fresh samples of LNT 1A and Comparative LNT 1B (1.38-inch diameter, 5-inch length cores) are subjected to an oxygen storage test, according to the following procedure. 5-inch cores of LNT 1A and Comparative LNT 1B are preconditioned at 600 °C in air for 1 hour before testing. Testing is performed on a synthetic gas rig with all testing done at a GHSV of 17,700 hr'¹. The temperature is then reduced to 200 °C under N₂ and 10 cycles of 30 seconds lean (1 vol.% O₂, balance N₂) and 30 seconds rich (2 vol.% CO, balance N₂) are performed to evaluate the oxygen storage capacity (OSC). The temperature is then ramped to 280 °C under nitrogen and the testing is repeated, followed by a ramping to 400 °C under nitrogen and the testing is repeated again. The oxygen storage capacity is then determined by calculation of the average O₂ removed by the catalyst from the inlet gas phase over the last 6 cycles of 30s lean operation.

LNT 1A and Comparative LNT 1B are then re-tested using the same procedure following ageing in a hydrothermal gas mix of 20% O₂, 10% H₂O, balance of N₂ at 800 °C for 5h. The results for 280 °C are shown in Table 1.

Table 1: OSC Results at 280 °C

Test Run	Oxygen consumption (mg/L)
Fresh	HT800 °C 5h aged
LNT1A	983	753
Comp. LNT 1B	1380	930

It can be seen from the results in Table 1 that LNT 1A has significantly less OSC compared to Comparative LNT 1B, indicating that LNT 1A would require a much shorter regeneration length as compared to Comparative LNT 1B.

Claims

Claims:

1. A ΝΟχ trap composition comprising a noble metal, a NOX storage component, a support, and a ceria-containing material, wherein the ceriacontaining material has a surface area of less than 80 m2/g.

2. The NOX trap composition of claim 1, wherein the ceria-containing material has a surface area of 40-75 m2/g.

3. The NOxtrap composition of claim 1 or claim 2 wherein the noble metal is selected from the group consisting of palladium, platinum, gold, rhodium, and mixtures thereof.

4. The NOX trap composition of any preceding claim wherein the NOX storage component comprises an alkaline earth metal, an alkali metal, a rare earth metal, or mixtures thereof.

5. The NOX trap composition of any preceding claim wherein the NOX storage component comprises barium, neodymium, lanthanum, or mixtures thereof.

6. The ΝΟχ trap composition of any preceding claim wherein the NOX storage component comprises barium.

7. The ΝΟχ trap composition of any preceding claim wherein the support is selected from the group consisting of alumina, silica, titania, zirconia, magnesia, niobia, tantalum oxide, molybdenum oxide, tungsten oxide, and a mixed oxide or composite oxide of any two or more thereof.

8. The ΝΟχ trap composition of any preceding claim wherein the support is a magnesia-alumina.

9. The ΝΟχ trap composition of any preceding claim wherein the ceriacontaining material is selected from the group consisting of a cerium oxide, a cerium-zirconium mixed oxide, and a ceria-zirconia-alumina

5 mixed oxide.

10. The NOX trap composition of any preceding claim wherein the NOX trap has an oxygen storage capacity that is reduced by greater than 40% compared to a fresh NOX that contains the ceria-containing material that

10 has not been pre-aged.

11. A ΝΟχ trap composition comprising a noble metal, a NOX storage component, a support, and a ceria-containing material, wherein the ceriacontaining material is pre-aged prior to incorporation into the NOX trap

15 composition.

12. The NOxtrap composition of claim 11 wherein the noble metal is selected from the group consisting of palladium, platinum, gold, rhodium, and mixtures thereof.

13. The ΝΟχ trap composition of claim 11 or claim 12 wherein the NOX storage component comprises an alkaline earth metal, an alkali metal, a rare earth metal, or mixtures thereof.

25

14. The ΝΟχ trap composition of any of claims 11 to 13 wherein the NOX storage component comprises barium, neodymium, lanthanum, or mixtures thereof.

15. The ΝΟχ trap composition of any of claims 11 to 14 wherein the NOX

30 storage component comprises barium.

16. The NOxtrap composition of any of claims 11 to 15 wherein the support is selected from the group consisting of alumina, silica, titania, zirconia, magnesia, niobia, tantalum oxide, molybdenum oxide, tungsten oxide, a mixed oxide or composite oxide of any two or more thereof.

17. The NOX trap composition of any one of claims 11 to 16 wherein the support is a magnesia-alumina.

18. The NOX trap composition of any of claims 11 to 17 wherein the ceria10 containing material is selected from the group consisting of a cerium oxide, a cerium-zirconium mixed oxide, and a ceria-zirconia-alumina mixed oxide.

19. The NOX trap of any of claims 11 to 18 wherein the ceria-containing

15 material has a surface area of less than 80 m2/g after pre-aging.

20. The NOX trap composition of any of claims 11 to 19, wherein the ceriacontaining material has a surface area of 40-75 m2/g.

20

21. A NOX trap catalyst comprising the NOX trap composition of any of claims

1 to 20 supported on a metal or ceramic substrate.

22. The NOxtrap catalyst of claim 21, wherein the substrate is a flow-through monolith or a filter monolith.

23. A NOX trap catalyst comprising the NOX trap composition of any of claims 1 to 20, wherein the composition is extruded to form a flow-through or filter substrate.

24. An emission treatment system for treating a flow of a combustion exhaust gas comprising the NOxtrap catalyst of any one of claims 21 to 23.

25. The emission treatment system of claim 24, wherein the internal

5 combustion engine is a diesel engine.

26. The emission treatment system of claim 24 or claim 25, further comprising a selective catalytic reduction catalyst system, a particulate filter, a selective catalytic reduction filter system, a passive NOX adsorber, a three10 way catalyst system, or combinations thereof.

27. A method of treating an exhaust gas from an internal combustion engine comprising contacting the exhaust gas with the NOX trap catalyst of any one of claims 21 to 23.

28. A method of reducing the oxygen storage capacity of a ceria-containing material in a NOX trap composition, comprising pre-aging the ceriacontaining material prior to incorporating it into the NOxtrap composition.

20

29. The method of claim 28, wherein the pre-aging is performed by heating the ceria-containing material at a temperature greater than 700 °C in the absence of added water.

30. The method of claim 28 or claim 29, wherein the pre-aging is performed

25 by heating the ceria-containing material at a temperature of between 750 and 950 °C in the absence of added water.

31. Use of a pre-aged ceria-containing material to reduce the oxygen storage capacity of a NOxtrap composition.

32. The use according to claim 31, wherein the ceria-containing material is pre-aged by heating the ceria-containing material at a temperature greater than 700 °C in the absence of added water.

5

33. The use according to claim 31 or claim 32, wherein the pre-aging is performed by heating the ceria-containing material at a temperature of between 750 and 950 °C in the absence of added water.

Intellectual

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Office

Application No: GB1614923.9 Examiner: Mr Jorge Quintero