Patent Description:
The largest portions of most combustion exhaust gases contain relatively benign nitrogen (N<NUM>), water vapor (H<NUM>O), and carbon dioxide (CO<NUM>); but the exhaust gas also contains in relatively small part noxious and/or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from un-burnt fuel, nitrogen oxides (NOx) from excessive combustion temperatures, and particulate matter (mostly soot). To mitigate the environmental impact of exhaust gas released into the atmosphere, it is desirable to eliminate or reduce the amount of these undesirable components, preferably by a process that, in turn, does not generate other noxious or toxic substances.

One of the most burdensome components to remove from a vehicular exhaust gas is NOx, which includes nitric oxide (NO), nitrogen dioxide (NO<NUM>), and/or nitrous oxide (N<NUM>O). The reduction of NOx to N<NUM> in a lean burn exhaust gas, such as that created by diesel engines, is particularly problematic because the exhaust gas contains enough oxygen to favor oxidative reactions instead of reduction. NOx can be reduced in a diesel exhaust gas, however, by a heterogenic catalysis process commonly known as Selective Catalytic Reduction (SCR). An SCR process involves the conversion of NOx,in the presence of a catalyst and with the aid of a reducing agent, into elemental nitrogen (N<NUM>) and water. In an SCR process, a gaseous reductant such as ammonia is added to an exhaust gas stream prior to contacting the exhaust gas with the SCR catalyst. The reductant is absorbed onto the catalyst and the NOx reduction reaction takes place as the gases pass through or over the catalyzed substrate. The chemical equation for stoichiometric SCR reactions using ammonia is:.

2NO + 4NH<NUM> + 2O<NUM> → 3N<NUM> + <NUM><NUM>O.

2NO<NUM> + 4NH<NUM> + O<NUM> → 3N<NUM> + <NUM><NUM>O.

NO + NO<NUM> + 2NH<NUM> → 2N<NUM> + <NUM><NUM>O.

Platinum Group Metal (PGM)-based reduction catalysts have been reported since the mid-<NUM>'s (<NPL>) to exhibit excellent NOx reduction activity at low temperatures. These catalysts, however, have very poor selectivity for N<NUM>, typically less than <NUM>%. At low temperatures, e.g. about <NUM> to about <NUM>, the low selectivity for N<NUM> correlates with the formation of significant amounts of N<NUM>O; while at high temperatures, e.g. greater than about <NUM>, the low selectivity correlates to the oxidation of NH<NUM> (the desired reductant) to NOx.

Another common problem with NOx reduction systems utilizing an NH<NUM> reductant is the release of unreacted ammonia, also referred to as "ammonia slip". Slip can occur when catalyst temperatures are not in the optimal range for the reaction or when too much ammonia is injected into the process. An additional oxidation catalyst is typically fitted downstream of an SCR system to reduce such slip. This catalyst typically contains a PGM component either in single catalyst configuration where the catalyst acts solely as an oxidation catalyst or in a dual catalyst configuration where zoning or layering of the catalyst allows for both oxidative and reductive functionality.

PGM purportedly has been incorporated into MCM-<NUM> , a mesoporous zeolite having a pore size between <NUM> - <NUM> Angstroms by incipient wetness for hydrocarbon SCR. Due to the large pore size, no shape selectivity for these catalysts has been observed. Park et al. studied this phenomenon, and concluded that if Pt was incorporated into the pores of ZSM-<NUM>, and <NUM>-ring, medium pore size zeolite, by a typical incipient wetness method, then some selectivity, e.g., conversion of NOx and N<NUM> yield would be expected. However, the catalysts made by this method show the same conversion of NOx and N<NUM> yield. Therefore, typical incipient wetness methods are not capable of achieving high PGM exchange or incorporate onto the walls of the molecular sieve crystal structure or into the walls by filling void space within the crystal structure itself.

These drawbacks of conventional PGM-based catalysts limit their practical application. There is, therefore a continuing unmet need for PGM based molecular sieve catalysts that can provide for high NOx reduction efficiency at low temperatures, high N<NUM> selectivity, and reduced NH<NUM> slip.

<NPL>) describes molecular shape discriminating catalytic reactions with crystalline aluminosilicate salts of the molecular sieve family. <NPL>) describes ruthenium containing small pore zeolites for shape selective catalysis. <NPL>) describes the introduction of noble metals into small pore zeolites via solid state ion exchange. <NPL>) describes incorporating platinum precursors into a NaA-zeolite synthesis mixture promoting the formation of nanosized zeolite. <NPL>) describes the contribution of hydrogen spillover to the hydrogenation of naphthalene over dilute Pt/RHO catalysts. <NPL>) describes small colloidal zeolites templated by Pd and Pt amines. <CIT> describes catalysts, methods and systems for treating diesel engine exhaust streams. <CIT> describes catalysts for treating transient NOx emissions.

Applicants have unexpectedly discovered that incorporating PGM into the porous network of a small pore molecular sieves achieves particularly good selectivity for N<NUM> during a selective catalytic reduction of NOx in a lean burn exhaust gas at temperatures of about <NUM> to about <NUM>, especially including temperatures of about <NUM> to about <NUM>. This result is surprising in view of the finding that the poor selectivity of PGM based NOx reduction catalysts is related to the inherent activity of the PGM species regardless of the support material, e.g. Al<NUM>O<NUM>, silica, molecular sieves. Conventional loading techniques, such as impregnation or solution ion-exchange, are well suited for embedding base metals into support materials. But PGMs cannot be incorporated into molecular sieves through the same processes without a significant amount of the metal depositing on the molecular sieve surface and not within the pores. It is believed that this surface PGM promotes N<NUM>O formation and thus reduced selectivity for N<NUM>. For example, the yield for N<NUM> in standard small pore molecular sieves with surface PGMs at temperatures from <NUM> to <NUM> is well below <NUM>%. In contrast to conventional PGM catalysts, applicants have found that molecular sieves embedded with PGMs using techniques such as those described herein, i.e., a majority of the PGM is incorporated into the pore network of the molecular sieve, the resulting catalyst achieves much higher selectivity for N<NUM>. The N<NUM> selectivity of the PGM embedded catalyst is greater than <NUM>%, and can be greater than <NUM>%, and even greater than about <NUM>%.

Moreover, the present catalysts also achieve particularly good ammonia oxidation at temperatures above <NUM>. Thus, the catalyst can serve the dual role of low temperature NOx reduction and high temperature ammonia oxidation. This dual functionality is particularly valuable in exhaust systems that also contain an upstream conventional SCR catalyst, which typically have a light-off temperature of at least <NUM>. In such systems, the PGM catalyst serves as an SCR during relatively cold conditions, such as engine start-up; and after the exhaust system heats-up, the PGM catalyst changes functionality to serve as an ammonia slip catalyst. Very high NOx conversion and high N<NUM> selectivity at temperatures below <NUM> and very high NH<NUM> oxidation at high temperatures is a rare combination of features for a single catalyst and is not present in other known exhaust gas treatment catalysts.

The invention is defined in the appended independent claims. Preferred embodiments are defined in the appended dependent claims. As defined in appended claim <NUM>, the present invention relates to a catalyst article comprising a catalyst disposed on a substrate, wherein the catalyst comprises (a) a small pore aluminosilicate molecular sieve material containing a maximum ring size of <NUM> comprising a plurality of crystals having a surface and a porous network; and (b) at least one metal selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Mo, W, Au and Ag, wherein at least about <NUM> weight percent of said metal is embedded in said porous network based on the total amount of said metal in and on said small pore aluminosilicate molecular sieve material, as measured by SEM imaging, wherein the substrate is a wall-flow filter or a flow-through monolith, wherein the small pore molecular sieve material has a framework selected from RHO and CHA. (Such catalyst, with or without other features described herein, are also referred to as "PGM catalyst".

According to another aspect of the invention, provided is catalyst article comprising the metal catalyst disposed on a substrate, as a wall-flow or flow through honeycomb monolith, preferably as a washcoat.

According to another aspect of the invention, provided is a method for treating emissions comprising (a) contacting a lean burn exhaust stream containing NOx and ammonia with a catalyst article according to claim <NUM> at a temperature of about <NUM> to about <NUM>; and (b) reducing at least a portion of said NOx to N<NUM> and H<NUM>O at a temperature of about <NUM> to about <NUM> and oxidizing at least a portion of said ammonia at a temperature of about <NUM> to about <NUM>.

According to another aspect of the invention, provided is a method for treating emissions comprising (a) contacting a lean burn exhaust stream containing CO and NO with a catalyst article according to claim <NUM>; and (b) oxidizing at least one of said CO and NO to form CO<NUM> and NO<NUM>, respectively, wherein said oxidizing NO to NO<NUM> results in an exhaust gas stream having an NO:NO<NUM> ratio of from about <NUM>:<NUM> to about <NUM>:<NUM> by volume.

According to yet another aspect of the invention, provided is a system for treating exhaust gas comprising (a) a reductant source; (b) an upstream SCR catalyst; and (c) a downstream catalyst article according to claim <NUM>; wherein said reductant source, upstream SCR catalyst, and downstream catalyst are in fluid communication with each other and are arranged so that an exhaust gas stream flowing through the system contacts the reductant source prior to the upstream SCR catalyst and contacts the SCR catalyst prior to the downstream catalyst article.

In a preferred embodiment, the invention is directed to a catalyst for improving environmental air quality, particularly for improving exhaust gas emissions generated by diesel and other lean burn engines. Exhaust gas emissions are improved, at least in part, by reducing NOx and/or NH<NUM> slip concentrations in lean burn exhaust gas over a broad operational temperature range. Useful catalysts are those that selectively reduce NOx and/or oxidize ammonia in an oxidative environment (i.e., an SCR catalyst and/or AMOX catalyst). The catalyst is also useful in oxidizing other exhaust system components such as CO and NO.

Provided is a catalyst composition comprising a small pore molecular sieve material embedded with PGM.

"PGM embedded" as used herein means PGM within at least a portion of the pore network of a molecular sieve, including PGM on the surface of the interior walls of the pore network, in the crystalline framework, and/or within pore voids (e.g., crystalline cages), for example when the molecular sieve is formed. PGM occupying void space within the structural framework of the crystal can be formed in situ during the synthesis of the molecular sieve. Examples include direct incorporation of PGM into the pores of the molecular sieves during synthesis (<NPL>; <NPL>). In a particular example, platinum can be incorporated into a small pore molecular sieve, such as RHO, during synthesis by adding a source of platinum, such as bis(enthylenediamine)platinum (II) chloride, to a sol gel precursor of the small pore aluminosilicate molecular sieve. In another example, a source of PGM, such as platinum nitrate or palladium nitrate, can be used to create a PGM-tetraethylenepentamine (TEPA) complex, which in turn can be used to synthesize small pore aluminosilicate molecular sieve having a CHA framework.

PGM within the network also can be achieved by certain non-solution ion exchange or isomorphous substitution. One such technique is solid state ion exchange of PGM into the pore of the molecular sieve (<NPL>). PGM residing on the surface of the pore network typically from via weakly associated bonds between the PGM and the surface within the pore (e.g., at acid sites).

A combination of in situ synthesis and exchange/substitution techniques can be used to increase the amount of PGM embedded molecular sieve catalyst.

"Molecular sieves" as used herein means a material having a pore network with one or more uniform pore sizes which results from the material's crystalline or quasi-crystalline framework, and includes aluminosilicates such as zeolites, silicoaluminophosphates, aluminophosphates, and combinations thereof as mixed-phase materials. A molecular sieve framework is defined in terms of the geometric arrangement of its primary tetrahedral atoms "T-atoms" (e.g., Al and Si). Each T-atom in the framework is connected to neighboring T-atoms through oxygen bridges and these or similar connections are repeated to form a crystalline structure. Codes for specific framework types are assigned to established structures that satisfy the rules of the IZA Structure Commission. The interconnection of tetrahedral species form internal cell walls that, in turn, define void pore volumes. The molecularly porous frameworks have volumes on the order of a few cubic nanometers and cell openings (also referred to as "pores" or "apertures") on the order of a few angstroms in diameter. The pores are aligned within the framework to create one or more channels which extend through the framework (pore network), thus creating a mechanism to restrict the ingress or passage of different molecular or ionic species through the molecular sieve, based on the relative sizes of the channels and molecular or ionic species.

The size and shape of molecular sieves affect their catalytic activity in part because they exert a steric influence on the reactants, controlling the access of reactants and products. For example, small molecules, such as NOx, can typically pass into and out of the cells and/or can diffuse through the channels of a small-pore molecular sieve (i.e., those having framework with a maximum ring size of eight tetrahedral atoms), whereas larger molecules, such as long chain hydrocarbons, cannot. Moreover, partial or total dehydration of a molecular sieve can results in a crystal structure interlaced with channels of molecular dimensions.

The cell openings can be defined by their ring size, where, for example, the term "<NUM>-ring" refers to a closed loop that is built from <NUM> tetrahedrally coordinated silicon (or aluminum) atoms and <NUM> oxygen atoms. Molecular sieves having a small pore framework, i.e., containing a maximum ring size of <NUM>, have been found to be particularly useful in SCR applications. In the present invention, the small pore molecular sieve has a framework selected from RHO and CHA.

Illustrative examples of suitable small pore molecular sieves are set out in Table <NUM>.

Small pore molecular sieves with particular application for treating NOx in exhaust gases of lean-burn internal combustion engines, e.g. vehicular exhaust gases, are set out in Table <NUM>.

It will be appreciated that such molecular sieves include synthetic crystalline or pseudo-crystalline materials that are isotypes (isomorphs) of one another via their defined framework. For example, specific CHA isotypes that are useful in the present invention include, but are not limited to, LZ-<NUM>, Linde D, Linde R, Phi, SAPO-<NUM>, SAPO-<NUM>, SAPO-<NUM>, SSZ-<NUM>, SSZ-<NUM>, and ZK-<NUM>, with SAPO-<NUM> and SSZ-<NUM> being most preferred.

As used herein, the term "SSZ-<NUM>" means aluminosilicates described in <CIT> (Zones) as well as any analogs thereof. As used herein, the term "analogs" with respect to a CHA isotype means a molecular sieve having the same topology and essentially the same empirical formula, but are synthesized by a different process and/or have different physical features, such as different distributions of atoms within the CHA framework, different isolations of atomic elements within the molecular sieve (e.g., alumina gradient), different crystalline features, and the like.

Useful aluminosilicates include framework metals other than aluminum, preferably a transition metal or a PGM (also known as metal substituted aluminosilicates). As used herein, the term "metal substituted" with respect to an aluminosilicate framework means the framework has one or more aluminum or silicon framework atoms replaced by the substituted metal. In contrast, the term "metal exchanged" means a molecular sieve having extra-framework metal ions and the term "metal embedded" means extra-framework metal ions within the molecular sieve interior vis-à-vis the exterior surface of the molecular sieve crystal. Metal substituted silico-aluminophosphate (also referred to as MeAPSO) molecular sieves likewise have a framework in which the substituted metal has been inserted.

In preferred embodiments, the molecular sieve material comprises a plurality of molecular sieve crystals having a mean crystal size of greater than about <NUM>, preferably between about <NUM> and about <NUM>, such as about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, and about <NUM> to about <NUM>. The crystals in the catalyst composition can be individual crystals, agglomeration of crystals, or a combination of both. As used herein, the crystal surface means the external surface of the crystal or external surface of an agglomeration of crystals.

Crystal size (also referred to herein as the crystal diameter) is the length of one edge of a face of the crystal. For example, the morphology of chabazite crystals is characterized by rhombohedral (but approximately cubic) faces wherein each edge of the face is approximately the same length. Direct measurement of the crystal size can be performed using microscopy methods, such as SEM and TEM. For example, measurement by SEM involves examining the morphology of materials at high magnifications (typically <NUM>× to <NUM>,<NUM>×). The SEM method can be performed by distributing a representative portion of the molecular sieve powder on a suitable mount such that individual particles are reasonably evenly spread out across the field of view at <NUM>× to <NUM>,<NUM>× magnification. From this population, a statistically significant sample of random individual crystals (e.g., <NUM> - <NUM>) are examined and the longest dimensions of the individual crystals parallel to the horizontal line of a straight edge are measured and recorded. (Particles that are clearly large polycrystalline aggregates should not be included the measurements. ) Based on these measurements, the arithmetic mean of the sample crystal sizes is calculated. Other techniques for determining mean particle size or crystal size, such as laser diffraction and scattering can also be used.

The relative amounts of alumina and silica in aluminosilicate molecular sieves can be characterized by a silica-to-alumina mole ratio (SAR). Preferred aluminosilicate molecular sieves have an SAR of about <NUM> to about <NUM>, such as about <NUM> to about <NUM>, and about <NUM> to about <NUM>. In certain embodiments, the aluminosilicate molecular sieve has an SAR of about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, and from about <NUM> to about <NUM>. In certain other embodiments the aluminosilicate molecular sieve has an SAR of about <NUM> to about <NUM>. The silica-to-alumina ratio of molecular sieves may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid atomic framework of the molecular sieve crystal and to exclude silicon or aluminum in the binder or, in cationic or other form, within the channels. It will be appreciated that it may be extremely difficult to directly measure the silica-to-alumina ratio of a molecular sieve after it has been combined with a binder material. Accordingly, the silica-to-alumina ratio has been expressed hereinabove in term of the silica-to-alumina ratio of the parent molecular sieve, i.e., the molecular sieve used to prepare the catalyst, as measured prior to the combination of this molecular sieve with the other catalyst components.

The molecular sieves preferably have an alkali content of less than <NUM> weight percent based on the total weight of the molecular sieve. As used here, the alkali content includes the total weight of alkali metals and alkaline earth metals, such as sodium, potassium, calcium, and magnesium, that are present in cationic form in the molecular sieve. In certain embodiments, the alkali content is less than about <NUM> weight percent, such as less than <NUM> weight percent, less than <NUM> weight percent, less than <NUM> weight percent, and less than <NUM> weight percent, based on the total weight of the molecular sieve.

As used herein, "PGM" means the traditional platinum group metals, i.e., Ru, Rh, Pd, OS, Ir, Pt, as well as other metals that are conventionally in similar catalytic applications, including Mo, W and precious metals such as Au and Ag. Preferred PGMs include Ru, Rh, Pd, OS, Ir, Pt, Pd, and Au, with Pt, Rh, and Pd being more preferred, and Pd and Pt being particularly preferred. In certain embodiments, the PGM comprises two or more metals, such as Pt and Pd; Pt, Pd, and Rh; Pd and Rh; Pd and Au; or single metals such as Pt, Pd, or Rh. For embodiments which utilize a combination of two or more metals, the ratio of each metal to the other is not particularly limited. In certain embodiments, the catalyst comprises a majority of Pt relative to other PGMs present in the catalyst, based on total weight of the PGMs. In certain, the catalyst comprises a majority of Pd relative to other PGMs present in the catalyst, based on total PGM weight. In certain embodiments which comprise Pt and Pd, the relative weight ratio of Pt:Pd is about <NUM>:<NUM> to about <NUM>:<NUM>, for example about <NUM>:<NUM> to about <NUM>:<NUM>, or about <NUM>:<NUM> to about <NUM>:<NUM>.

In certain embodiments, the catalyst comprises <NUM> to about <NUM> weight percent PGM relative to the weight of the molecular sieve carrier. For example, the catalyst can comprise <NUM> to about <NUM> weight percent PGM, about <NUM> to about <NUM> weight percent PGM, about <NUM> to about <NUM> weight percent PGM, about <NUM> to about <NUM> weight percent PGM, or about <NUM> to about <NUM> weight percent PGM.

To achieve high selectivity for N<NUM> over N<NUM>O, a majority of the PGM in the catalyst is preferably embedded within the molecular sieve crystals instead of disposed on the surface of the crystals. In the present invention, at least about <NUM> weight percent of the PGM is embedded in said porous network based on the total PGM in and on the molecular sieve material. For example, in certain embodiments, at least about <NUM> weight percent, at least about <NUM> weight percent, at least about <NUM> weight percent, or at least about <NUM> weight percent of the PGM is embedded in said porous network based on the total PGM in and on the molecular sieve material. In certain embodiments, substantially all of the PGM is embedded in the molecular sieve, and by corollary the surface of the crystals are substantially free of PGM. By substantially free of PGM, it is meant that the amount of PGM, if any, is de minimus and therefore does not affect the relevant catalytic properties of the material by a degree that can be detected by standard commercial techniques. In certain embodiments, the catalyst crystals are free of external PGM as measure by SEM imaging (i.e., spectral mapping).

Although it can be difficult to quantitatively measure the nature and quantity of PGMs embedded into the small pores of the molecualr sieve, the relative amount of embedded PGM can be inferred through performance (e.g., N<NUM> selectivity). Typically, the selectivity for N<NUM> in standard small pore molecular sieves with surface PGMs at temperatures from <NUM> to <NUM> are well below <NUM>%. In the present invention, the selectivity or performance of the PGM embedded catalyst is greater than <NUM>%, preferably greater than about <NUM>%, greater than about <NUM>%, greater than about <NUM>%, greater than about <NUM>%, greater than about <NUM>%, or greater than about <NUM>% due to embedding PGMs within the pores as described herein.

In certain embodiments, the ratio of PGM embedded in the porous network of the molecular sieve relative to the PGM on the crystal surface is about <NUM>:<NUM> to about <NUM>:<NUM>, for example about <NUM>:<NUM> to about <NUM>:<NUM>, about <NUM>:<NUM> to about <NUM>:<NUM>, or about <NUM>:<NUM> to about <NUM>:<NUM>.

In certain embodiments, the PGM embedded in the porous structure is exchanged PGM and/or free PGM ions. In certain embodiments, a majority, or substantially all, of the PGM embedded in the porous structure is exchanged PGM on the interior surface walls. In certain embodiments, a majority, or substantially all, of the PGM embedded in the porous structure is free PGM ions in said void pore volumes.

In addition to PGM, the molecular sieve material can also comprise one or more transition metals, such as copper, nickel, zinc, iron, tungsten, molybdenum, cobalt, titanium, zirconium, manganese, chromium, vanadium, niobium, as well as tin, bismuth, and antimony. These additional metals are preferably present as extra-framework metals. Preferred transition metals are base metals, and preferred base metals include those selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and copper, and combinations thereof. In a preferred embodiment, at least one of the extra-framework metals is copper. Other preferred extra-framework metals include iron, particularly in combination with copper.

Transition metals can be added to molecular sieves by any conventional processes, including ion exchange, spray drying, incipient wetness, and the like. Preferably, the transition metal is present in an amount, and is added by a technique, that does not interfere with the concentration of the PGM in the molecular sieve. In certain embodiments, the transition metal is present in a concentration of about <NUM> to about <NUM> percent by weight, more preferably from about <NUM> to about <NUM> percent by weight, for example about <NUM> to about <NUM> percent by weight or about <NUM> to about <NUM> percent by weight, based on the weight of the molecular sieve.

The catalyst for use in the present invention can be in the form of a washcoat, preferably a washcoat that is suitable for coating a substrate, such as a metal or ceramic flow through monolith substrate or a filtering substrate, i.e. a wall-flow filter Accordingly, provided is a washcoat comprising a catalyst component as described herein. In addition to the catalyst component, washcoat compositions can further comprise a binder selected from the group consisting of alumina, silica, (non-zeolite) silica-alumina, naturally occurring clays, TiO<NUM>, ZrO<NUM>, and SnO<NUM>. Other washcoat additives include stabilizers and promoters. These additional components do not necessarily catalyze the desired reaction, but instead improve the catalytic material's effectiveness, for example by increasing its operating temperature range, increasing contact surface area of the catalyst, increasing adherence of the catalyst to a substrate, etc. Typical PGM loadings for washcoated SCR applications range from about <NUM>/ft3 (<NUM>/L) to about <NUM>/ft3 (<NUM>/L), more preferably about <NUM>/ft3 (<NUM>/L) to about <NUM>/ft3 (<NUM>/L), such as about <NUM>/ft3 (<NUM>/L) to about <NUM>/ft3 (<NUM>/L) or about <NUM>/ft3 (<NUM>/L) to about <NUM>/ft3 (<NUM>/L). The total amount of washcoated SCR catalyst component will depend on the particular application, but could comprise about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L), about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L), about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L), about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L), or about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L) of the SCR catalyst. Preferred washcoat loading for the SCR catalyst is from about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L) or about <NUM> to about <NUM>/in<NUM> (about <NUM> to about <NUM>/L).

In the present invention, provided is an article comprising a substrate upon which the catalyst is deposited. The coating process may be carried out by methods known per se, including those disclosed in <CIT>. The substrates is a wall-flow filters, such as wall-flow ceramic monoliths, or flow through substrates, such as metal or ceramic foam or fibrous filters. In addition to cordierite, silicon carbide, silicon nitride, ceramic, and metal, other materials that can be used for the substrate include aluminum nitride, silicon nitride, aluminum titanate, α-alumina, mullite e.g., acicular mullite, pollucite, a thermet such as Al<NUM>OsZFe, Al<NUM>O3/Ni or B<NUM>CZFe, or composites comprising segments of any two or more thereof. Preferred materials include cordierite, silicon carbide, and alumina titanate.

Preferred substrates for use in mobile application are monoliths having a so-called honeycomb geometry which comprises a plurality of adjacent, parallel channels, wherein each channel typically has a square cross-sectional area. The honeycomb shapes provide a large catalytic surface with minimal overall size and pressure drop. The actual shape and dimensions of the filter substrate, as well as properties such as channel wall thickness, porosity, etc., depend on the particular application of interest. In certain embodiments, the substrate has up to about <NUM> channels (cells) per square inch of cross section ("cpsi"), for example about <NUM> to about <NUM> cpsi or about <NUM> to about <NUM> cpsi.

Particular combinations of filter mean pore size, porosity, pore interconnectivity, and washcoat loading can be combined to achieve a desirable level of particulate filtration and catalytic activity at an acceptable backpressure. Porosity is a measure of the percentage of void space in a porous substrate and is related to backpressure in an exhaust system: generally, the lower the porosity, the higher the backpressure. Preferably, the porous substrate has a porosity of about <NUM> to about <NUM>%, for example about <NUM> to about <NUM>%, about <NUM> to about <NUM>%, or from about <NUM> to about <NUM>%.

Pore interconnectivity, measured as a percentage of the substrate's total void volume, is the degree to which pores, void, and/or channels, are joined to form continuous paths through a porous substrate, i.e., from the inlet face to the outlet face. In contrast to pore interconnectivity is the sum of closed pore volume and the volume of pores that have a conduit to only one of the surfaces of the substrate. Preferably, the porous substrate has a pore interconnectivity volume of at least about <NUM>%, more preferably at least about <NUM>%.

The mean pore size of the porous substrate is also important for filtration. Mean pore size can be determined by any acceptable means, including by mercury porosimetry. The mean pore size of the porous substrate should be of a high enough value to promote low backpressure, while providing an adequate efficiency by either the substrate per se, by promotion of a soot cake layer on the surface of the substrate, or combination of both. Preferred porous substrates have a mean pore size of about <NUM> to <NUM>, for example about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, and about <NUM> to about <NUM>. In other embodiments, the mean pore size of the filter is about <NUM> to about <NUM>.

Wall flow filters for use with the present invention preferably have an efficiency of least <NUM>%, at least about <NUM>%, at least about <NUM>%, or at least about <NUM>%. In certain embodiments, the efficiency will be from about <NUM> to about <NUM>%, about <NUM> to about <NUM>%, about <NUM> to about <NUM>%, or about <NUM> to about <NUM>%. Here, efficiency is relative to soot and other similarly sized particles and to particulate concentrations typically found in conventional diesel exhaust gas. For example, particulates in diesel exhaust can range in size from <NUM> microns to <NUM> microns. Thus, the efficiency can be based on this range or a sub-range, such as <NUM> to <NUM> microns, <NUM> to <NUM> microns, or <NUM> to <NUM> microns. Preferred porosity for cordierite filters is from about <NUM> to about <NUM> %.

In certain embodiments, the catalyst is coated on a substrate in an amount sufficient to reduce the NOx and/or to oxidize ammonia contained in an exhaust gas stream flowing through the substrate or perform other functions such as conversion of CO into CO<NUM>.

The catalyst described herein can promote the low temperature reaction of a reductant, preferably ammonia, with nitrogen oxides to selectively form elemental nitrogen (N<NUM>) and water (H<NUM>O) vis-à-vis the competing reaction of oxygen and ammonia and also oxidize ammonia with oxygen or reduce ammonia to N<NUM>.

In certain embodiments, a conventional SCR catalyst and a PGM catalyst are used in series, for example on two separate substrates or on a single substrates as zones or layers. Preferably, the conventional SCR catalyst is disposed upstream of the PGM catalyst relative to the typical direction of exhaust gas flow past the catalysts. The conventional SCR catalyst preferably is a PGM-free catalyst. Examples of useful conventional SCR catalyst include those comprising a molecular sieve, such as BEA, CHA, ZSM-<NUM>, and the like, promoted with a transition metal, such as copper or iron, or comprising vanadium or vanadium/tungsten on a high surface area support such as alumina.

Turning to <FIG>, shown is an embodiment of the invention comprising a substrate <NUM>, such as a flow-through monolith, having an inlet <NUM> and an outlet <NUM> relative to the direction of exhaust gas flow <NUM> through the substrate. The inlet comprises a conventional SCR catalyst zone <NUM>, while the substrate outlet comprises an PGM catalyst zone <NUM>. As used herein, the term "zone" means a distinct catalytic area within and/or on the substrate. For example, a zone can be an area of the substrate in which a catalyst has permeated or a catalyst layer residing on top of and/or within substrate. The zone can be a discrete area, completely separated from other zones, can be adjacent to, or overlap with, other zones, or can be partially fused into other zones. The term "inlet" means the side, face, surface, channel, and/or portion of the substrate into which an exhaust gas typically flows from an external source. The term "outlet" means the side, face, surface, channel, and/or portion of the substrate from which an exhaust gas typically exits the filter. The phrase "on the inlet" and "on the outlet", with respect to the orientation of a catalytic zone and a substrate, is meant to include a catalyst residing as a zone or layer on top of the substrate face and/or within the substrate walls (i.e., within the pores of the substrate walls).

<FIG> shows a wall-flow filter <NUM> having inlet channels <NUM> and outlet channels <NUM> which are defined by a gas permeable walls <NUM> and gas impermeable inlet caps <NUM> and outlet caps <NUM>. Exhaust gas having a direction of flow <NUM> enters the filter <NUM> via one or more of the inlet channels <NUM>, passes through the gas permeable walls <NUM> which separate the inlet and outlet channels, and then exits the filter via the outlet channels <NUM>. The exhaust gas entering the inlet channels typically comprises soot, NOx, and preferably also contains a nitrogenous reducing agent, such as NH<NUM>, which is used to convert the NOx into other gases via an SCR reaction. Prior to passing through the gas permeable wall, at least a portion of the particulate matter in the exhaust gas is trapped at the inlet where it contacts the conventional SCR zone <NUM>. The conventional SCR zone facilitates a high-temperature SCR reaction, for example at about <NUM> to about <NUM> or about <NUM> to about <NUM>. As the exhaust gas passes through the conventional SCR catalyst zone, at least a portion of the NOx reacts with NH<NUM> in the presence of the SCR catalyst, wherein the NOx is reduced to N<NUM> and other gases. As the gas passes through the filter wall, it contacts the PGM catalyst <NUM> which facilitates a low-temperature SCR reaction, for example at about <NUM> to about <NUM> or about <NUM> to about <NUM> and a high-temperature AMOX reaction, for example at <NUM> to about <NUM>, about <NUM> to about <NUM>, or about <NUM> to about <NUM>.

In certain embodiments, the two zones converge between the inlet and outlet, while in other embodiments they are spatially separated. The zones on the inlet and outlet may exist as a coating on the surface of the filter substrate or may diffuse or permeate into all or a portion of the filter substrate. In a particularly preferred embodiment, the conventional SCR catalyst zone and the PGM catalyst zone permeate into opposite sides of the wall of a wall-flow filter. That is, the conventional SCR catalyst zone is created via the conventional SCR catalyst permeating into the wall from the inlet channel side of the wall and the PGM catalyst zone is created via the PGM catalyst permeating into the wall from the outlet channel side of the wall.

Turning to <FIG>, shown is a wall-flow filter <NUM> having inlet channels <NUM> and outlet channels <NUM> which are defined by a gas permeable walls <NUM> and gas impermeable inlet caps <NUM> and outlet caps <NUM>. Exhaust gas having a direction of flow <NUM> enters the filter <NUM> via one or more of the inlet channels <NUM>, passes through the gas permeable walls <NUM> which separate the inlet and outlet channels, and then exits the filter via the outlet channels <NUM>. The exhaust gas entering the inlet channels typically comprises soot, NOx, and preferably also contains a nitrogenous reducing agent, such as NH<NUM>, which is used to convert the NOx into other gases via an SCR reaction. As the exhaust gas passes through the gas permeable wall, at least a portion of the particulate matter in the exhaust gas is trapped at the inlet where it contacts the soot oxidation zone <NUM>. The soot oxidation zone facilitates an oxidation reaction wherein solid, carbonaceous particles of the soot are converted into gases, such as CO<NUM> and water vapor, which then pass through the gas permeable filter wall.

On the outlet side of the filter wall is a layered catalyst arrangement comprising a conventional SCR catalyst and a PGM catalyst disclosed herein, wherein the conventional SCR catalyst is disposed as a layer between the filter wall and the PGM catalyst is disposed as a layer on top of the SCR catalyst layer so that the exhaust gas flowing through the filter contacts the conventional SCR catalyst layer prior to the PGM catalyst layer. As the exhaust gas passes through the layered catalyst <NUM>, at least a portion of the NOx is reduced to N<NUM> and other gases over a wide temperature range (e.g., <NUM> to <NUM>) and ammonia slipping past the conventional SCR catalyst layer is oxidized by the PGM catalyst at temperatures greater than about <NUM>.

Provided is a method for reducing NOx compounds and/or oxidizing NH<NUM> in an exhaust gas, which comprises contacting the gas with a catalyst composition described herein for a time sufficient to reduce the level of NH<NUM> and/or NOx compounds in the gas. In one embodiment, nitrogen oxides are reduced with the reducing agent at a temperature of at least about <NUM>. In another embodiment, the nitrogen oxides are reduced with the reducing agent at a temperature from about <NUM> to about <NUM>. In a particular embodiment, the temperature range for an SCR reaction is from about <NUM> to about <NUM>. In a temperature range of about <NUM> to about <NUM>, and particularly between about <NUM> and about <NUM>, the selectivity for N<NUM> in the SCR reaction is at least about <NUM>%, for example at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, or about <NUM>%. In the same temperature ranges, the conversion of NOx to N<NUM> and H<NUM>O using the small pore molecular sieve catalyst embedded with PGM as described herein is at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, or at least about <NUM>%, particularly under conventional test conditions for commercial development of a diesel engine catalyst, including for example at a gas hourly space velocity of from about <NUM>,<NUM> hr-<NUM> to about <NUM>,<NUM> hr-<NUM>, optionally from about <NUM>,<NUM> hr-<NUM> to about <NUM>,<NUM> hr-<NUM>. In certain embodiments, the small pore molecular sieve catalyst embedded with PGM as described herein has higher or substantially similar (i.e., within <NUM>%) NOx conversion compared to an aluminosilicate chabazite catalyst having an SAR of <NUM> and containing <NUM> weight percent exchanged copper under similar test conditions.

Methods disclosed herein may comprise one or more of the following steps: (a) accumulating and/or combusting soot that is in contact with the inlet of a catalytic filter; (b) introducing a nitrogenous reducing agent into the exhaust gas stream prior to contact with wall-flow filter containing a PGM embedded small pore catalyst described herein; (c) generating NH<NUM> over a NOx adsorber catalyst, and preferably using such NH<NUM> as a reductant in a downstream SCR reaction; (d) contacting the exhaust gas stream with a Diesel Oxidation Catalyst (DOC) to oxidize hydrocarbon based soluble organic fraction (SOF) and/or carbon monoxide into CO<NUM>, and/or oxidize NO into NO<NUM>, which in turn, may be used to oxidize particulate matter in particulate filter; and/or reduce the particulate matter (PM) in the exhaust gas; (e) contacting the exhaust gas with one or more flow-through SCR catalyst device(s) in the presence of a reducing agent to reduce the NOx concentration in the exhaust gas; and (f) contacting the exhaust gas with an ASC catalyst, preferably downstream of a conventional SCR catalyst to oxidize most, if not all, of the ammonia prior to emitting the exhaust gas into the atmosphere or passing the exhaust gas through a recirculation loop prior to exhaust gas entering/re-entering the engine.

The reductant (also known as a reducing agent) for SCR processes broadly means any compound that promotes the reduction of NOx in an exhaust gas. Examples of reductants useful in the present invention include ammonia, hydrazine or any suitable ammonia precursor, such as urea ((NH<NUM>)<NUM>CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate, and hydrocarbons such as diesel fuel, and the like. Particularly preferred reductant, are nitrogen based, with ammonia being particularly preferred.

In another embodiment, all or at least a portion of the nitrogen-based reductant, particularly NH<NUM>, can be supplied by a NOx adsorber catalyst (NAC), a lean NOx trap (LNT), or a NOx storage/reduction catalyst (NSRC), disposed upstream of an SCR catalyst. Useful NAC components include a catalyst combination of a basic material (such as alkali metal alkaline earth metal or a rare earth metal, including oxides of alkali metals, oxides of alkaline earth metals, and combinations thereof), and a precious metal (such as platinum), and optionally a reduction catalyst component, such as rhodium. Specific types of basic material useful in the NAC include cesium oxide, potassium oxide, magnesium oxide, sodium oxide, calcium oxide, strontium oxide, barium oxide, and combinations thereof. The precious metal is preferably present at about <NUM> to about <NUM>/ft<NUM> (about <NUM> to about <NUM>/L), such as <NUM> to <NUM>/ft<NUM> (<NUM> to <NUM>/L). Alternatively, the precious metal of the catalyst is characterized by the average concentration which may be from about <NUM> to about <NUM> grams/ft<NUM> (about <NUM> to about <NUM>/L). In certain embodiments, the NAC comprises a PGM catalyst as disclosed herein.

Under certain conditions, during the periodically rich regeneration events, NH<NUM> may be generated over a NOx adsorber catalyst. The SCR catalyst downstream of the NOx adsorber catalyst may improve the overall system NOx reduction efficiency. In the combined system, the SCR catalyst is capable of storing the released NH<NUM> from the NAC catalyst during rich regeneration events and utilizes the stored NH<NUM> to selectively reduce some or all of the NOx that slips through the NAC catalyst during the normal lean operation conditions.

The method can be performed on a gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil fired power plants. The method may also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, etc. In a particular embodiment, the method is used for treating exhaust gas from a vehicular lean burn internal combustion engine, such as a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.

Provided is an exhaust system for a vehicular lean burn internal combustion engine, which system comprising a conduit for carrying a flowing exhaust gas, a source of nitrogenous reductant, a PGM catalyst described herein. The system can include a controller for the metering the nitrogenous reductant into the flowing exhaust gas only when it is determined that the PGM catalyst is capable of catalyzing NOx reduction at or above a desired efficiency, such as at above <NUM>. The determination by the control means can be assisted by one or more suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the exhaust gas, the quantity of fuel injected in the engine, the position of the exhaust gas recirculation (EGR) valve and thereby the amount of EGR and boost pressure.

In a particular embodiment, metering is controlled in response to the quantity of nitrogen oxides in the exhaust gas determined either directly (using a suitable NOx sensor) or indirectly, such as using pre-correlated look-up tables or maps--stored in the control means--correlating any one or more of the abovementioned inputs indicative of a condition of the engine with predicted NOx content of the exhaust gas. The metering of the nitrogenous reductant can be arranged such that <NUM>% to <NUM>% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at <NUM>:<NUM> NH<NUM>/NO and <NUM>:<NUM> NH<NUM>/NO<NUM>. The control means can comprise a pre-programmed processor such as an electronic control unit (ECU).

In a further embodiment, the PGM embedded small pore molecular sieve is provided as oxidation catalyst for oxidizing nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a point of metering the nitrogenous reductant into the exhaust gas. In one embodiment, the oxidation catalyst is adapted to yield a gas stream entering the SCR catalyst having a ratio of NO to NO<NUM> of from about <NUM>:<NUM> to about <NUM>:<NUM> by volume, e.g. at an exhaust gas temperature at oxidation catalyst inlet of <NUM> to <NUM>. The oxidation catalyst is preferable coated on a flow-through monolith substrate. In one embodiment, the at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium. The PGM catalyst can further be used to oxidize other components of an exhaust gas, including conversion of carbon monoxide into carbon dioxide.

In another embodiment, the PGM catalyst disclosed herein can be used in a three-way-catalyst (TWC) in gasoline or other rich burn engines.

Further, there is provided a vehicular lean-burn engine comprising an exhaust system according to the present invention. The vehicular lean burn internal combustion engine can be a diesel engine, a lean-burn gasoline engine or an engine powered by liquid petroleum gas or natural gas.

A first solution was prepared by mixing <NUM> of sodium hydroxide and <NUM> of H<NUM>O into a <NUM> PTFE cup designed to fit into an acid digestion vessel (Parr Instrument Company). <NUM> of aluminum hydroxide were added to the first solution. The resulting mixture was stirred until a homogeneous solution was obtained. <NUM> of cesium hydroxide solution (<NUM> wt. %) were added to the resulting mixture. Then, <NUM> of bis(enthylenediamine)platinum (II) chloride were added once the cesium hydroxide solution was incorporated. The mixture was stirred until homogeneous and <NUM> of AS-<NUM> Ludox were slowly added and blended into the mixture. The mixture was heated at <NUM> for <NUM> day. The solids were recovered by filtration. The composition of the recovered material is provided below:.

The synthesized Pt-RHO contain <NUM> wt. % Pd and XRD analysis confirmed that the zeolite comprised an RHO framework. SEM imaging demonstrated that no external Pt by spectral mapping, though Cs was present on the crystal surfaces.

A source of alumina and a base will be combined and dissolved in water. Then platinum nitrate will be added followed by the addition of tetraethylenepentamine (TEPA). The mixture will be stirred for about an hour and then a source of silica (e.g. silica sol) will be added drop-wise while stirring continues. The resulting gel will be stirred for another three hours and then will be transferred to a Teflon-lined stainless steel autoclave where it will be heated at <NUM> for about <NUM> days. The product will be recovered, filtered, washed, and then dried at <NUM> for about <NUM> hours. The resulting product will be tested via SEM to confirm that platinum is embedded in the CHA framework.

This procedure will be repeated except that the platinum nitrate will be substituted for palladium nitrate and the resulting product will be tested via SEM to confirm that palladium is embedded in the CHA framework.

The PGM embedded molecular sieves powders produced in examples <NUM> and <NUM> above will be tested for N<NUM> Selectivity / NOx Conversion / NH<NUM> Oxidation. A portion of each of the powder samples will be hydrothermally aged at <NUM> for <NUM> hours and another portion of the powder sample will be hydrothermally aged at <NUM> for <NUM> hours. Samples of the fresh powders and the aged powders will be exposed to a simulated diesel engine exhaust gas that will be combined with ammonia to produce a stream having an ammonia to NOx ratio (ANR) of <NUM> and a space velocity of <NUM>,<NUM> per hour. The catalyst's capacity for NOx conversion will be determined at temperatures ranging from about <NUM> to about <NUM>. The catalyst capacity for NH3 conversion will be determined at temperatures ranging from about <NUM> to about <NUM>.

Claim 1:
A catalyst article comprising a catalyst disposed on a substrate, wherein the catalyst comprises:
a. a small pore aluminosilicate molecular sieve material containing a maximum ring size of <NUM> comprising a plurality of crystals having a surface and a porous network; and
b. at least one metal selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Mo, W, Au and Ag,
wherein at least about <NUM> weight percent of said metal is embedded in said porous network based on the total amount of said metal in and on said small pore aluminosilicate molecular sieve material, as measured by SEM imaging,
wherein the substrate is a wall-flow filter or a flow-through monolith,
wherein the small pore molecular sieve material has a framework selected from RHO and CHA.