BACKGROUND

A. ) Field of Use:

The present invention relates to catalysts, systems, and methods that are useful for treating an exhaust gas that is produced during combustion of hydrocarbon fuel, particularly a lean burn exhaust gas containing soot and nitrogen oxides produced by a diesel engine.

B. ) Description of Related Art:

Exhaust gas is generated during the combustion of fuels such as natural gas, gasoline, diesel fuel, fuel oil or coal. When the combustion occurs in a chamber such as an engine or furnace, the resulting exhaust gas is typically treated prior to being discharged into the atmosphere through an exhaust pipe, flue gas stack or the like. The largest portion of exhaust gas consists of nitrogen (N ₂ ), water vapor (H ₂ 0), and carbon dioxide (C0 ₂ ); but untreated exhaust gas also contains, in relatively small part, undesirable noxious and/or toxic substances, such as carbon monoxide (CO) from incomplete combustion, hydrocarbons (HC) from un-burnt fuel, nitrogen oxides (NO _x ) (e.g., nitric oxide (NO), nitrogen dioxide (N0 ₂ ), and nitrous oxide (N ₂ 0)) from excessive combustion temperatures, and particulate matter (insoluble carbon soot particles, liquid hydrocarbons (e.g. lube oil and unburned fuel), and a soluble organic fraction. Of particular relevance to the present invention is exhaust gas emitted from diesel engines which typically operate using a high air-to-fuel ratio (i.e., very lean conditions). Such lean burn conditions often result in an exhaust gas with relatively high emissions of particulate matter and NO _x - two components which have proved to be difficult to efficiently convert into more benign substances.

Diesel engines are often equipped with exhaust systems that include one or more catalytic components which work separately or in combination to treat exhaust gas prior to its emission into the atmosphere. For example, it is known that NO _x can be converted into elemental nitrogen, N ₂ , and water by reacting the NO _x in the exhaust gas with N H ₃ in the presence of certain supported catalysts via a process commonly referred to as selective catalytic reduction (SCR). Known SCR catalysts include vanadium (V ₂ 0 ₅ ) carried by a mixture of ceria (Ce0 ₂ ) and alumina (Al ₂ 0 ₃ ) on a support (see EP 0 246 859), or V ₂ 0 ₅ /W0 ₃ supported on Ti0 ₂ (see WO 99/39809). Other SCR catalysts have also been proposed such as mixed metal oxides such as Fe-W/CeZr0 ₂ (WO 2009/001 131 ) and aluminosilicate and silicoaluminophosphate molecular sieves loaded with an extra-framework metal such as Cu:SAPO-34 (US 201 0/0290963).

Unlike NO _x treatment, soot remediation in an exhaust gas typically involves mechanical filtration. For example, soot emissions can be reduced by passing a soot-containing exhaust gas through a diesel particulate filter (DPF), such as a cordierite wall-flow filter (US 2010/0170230). However, the accumulation of soot particles on or in the filter can cause an undesirable increase in the back pressure across the filter which typically leads to decreased engine performance and efficiency. To regenerate the filter, the accumulated carbon-based soot must be removed from the filter which is typically accomplished by periodically combusting the soot. One such combustion technique involves catalytic oxidation of the soot at low temperatures via a soot oxidation catalyst incorporated onto the filter (i.e., a catalytic soot filter (CSF)). (US 4,902,487).

Conventional exhaust systems comprise separate components for NO _x treatment (SCR) and soot treatment (CSF). Yet it is often desirable to design individual exhaust components to perform more than one function in order to reduce the total space required by the exhaust system, reduce costs, etc. For example, applying an SCR catalyst to a filter substrate (SCRF) serves to reduce the overall size of an exhaust treatment system by allowing one substrate to serve two functions, namely catalytic conversion of NO _x by the SCR catalyst and removal of soot by the filter. For example, US Pat. Pub. 2010/01 80580 discloses an SCR catalyst can be applied to a wall-flow DPF. However, removal of the soot oxidation catalyst in an SCRF requires the soot accumulated at the filter surface to be burned at very high temperatures. High temperature SCR catalysts, such as Cu:SAPO-34, are available but are insoluble in water and thus, these catalysts must be applied to the filter as a viscous washcoat. Coating the filter with thick catalyst slurry causes a significant increase in backpressure and a corresponding reduction in fuel economy and engine power. Moreover, a combination of conventional SCR and oxidation catalysts is not feasible because it results in localized competition for N0 ₂ , thereby reducing the conversion efficiency of the SCR catalyst.

Accordingly, there remains a need for an efficient system for treating soot and NOx in lean burn exhaust gas. This invention satisfies that need among others. SUMMARY OF THE INVENTION

The present inventors have discovered a dual function catalytic filter which, in certain embodiments, has a soot burning catalyst on the filter inlet and an SCR catalyst on the filter outlet. By coating a filter substrate with a soot oxidation catalyst capable of burning particulates on the inlet channels and a SCR washcoat on the outlet channels, the complexity, size, and cost of an exhaust gas treatment system can be reduced. Moreover, the present inventors have discovered that certain soot oxidation catalysts will not consume nitrogen-based reductants (urea, ammonia, etc.) that are required for the downstream SCR reaction. Therefore, the present invention allows a reductant to be dosed into the exhaust gas upstream of the filter containing the soot oxidation catalyst. Additionally, in certain embodiments, the separation of the soot oxidation catalyst and the SCR catalyst will prevent localized competition for N0 ₂ and improve overall activity. Other advantages of the invention include less backpressure and better overall emission and engine performance compared to conventional systems that utilize separate catalyzed soot filters or SCR catalysts loaded on filter without a soot oxidation catalyst. Thus, such systems can be used to meet more stringent emission requirements that may be imposed by regulatory agencies.

Further improvements in performance can be obtained by integrating the dual function catalytic filter with an upstream diesel oxidation catalyst and at least one downstream SCR flow-through catalyst followed by an ammonia slip catalyst. Thus, in certain preferred embodiments, the dual function catalytic filter is a part of an exhaust treatment system that also includes an upstream diesel oxidation catalyst, at least one additional downstream SCR catalyst and a downstream ammonia slip catalyst.

Accordingly, provided is an article for treating an exhaust gas comprising (a) a soot filter having an inlet and an outlet; (b) a soot oxidation zone on the inlet, wherein the soot oxidation zone comprises a soot oxidation catalytic component consisting essentially of at least one transition metal dispersed on a cerium and zirconium mixed and/or composite oxide, wherein the at least one transition metal is selected from the group consisting of a Group VIB metal, a Group IB metal, a Group IVA metal, a Group VB metal, a Group VI IB metal, a Group VI II metal, and combinations thereof; and (c) an SCR zone coated on the outlet, wherein the SCR zone comprises an SCR catalytic component.

The inventors have found soot oxidation activity generally increases as the relative concentration of Zr0 ₂ to Ce0 ₂ increases. In certain preferred embodiments, the soot oxidation catalyst component has a formula of M:Ce _x 0 ₂ Zr ₁ . _x 0 ₂ , wherein x = about 0.1 to about 0.9 or about 0.99 and M is selected from W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, with W being most preferred. In certain preferred embodiments x is < about 0.7, preferably < about 0.5, more preferably < about 0.3, such as < about 0.25, < 0.20, or < about 0.15. In certain embodiments, x < about 0.1 , such as < about 0.07, < about 0.05, < about 0.03, or < about 0.01 , provided that x is > 0.001 or > about 0.005.

Certain SCR catalyst components have a formula of M :Ce _x 0 ₂ Zr ₁ . _x 0 ₂ , wherein x = about 0.1 to about 1 .0, with x is > about 0.3 being preferred, x > about 0.5 being more preferred, and x > about 0.7 being even more preferred; and M is selected from W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, with Fe and W being most preferred. For embodiments that include W in the SCR catalyst, the inventors have found that SCR activity increases with increasing Ce0 ₂ concentration, increases with increasing W concentration, and particularly that SCR activity increases with the combination of increasing Ce0 ₂ concentration and increasing W concentration. I n certain embodiments, the value of x for the SCR catalyst is > about 0.9, such as 0.95, 0.99, or 1 .00. I n certain preferred embodiments, the SCR catalyst is doped with at least two metals, W > about 25 wt. %, > about 50%, > about 75%, > 90 wt. %, or > 95 wt. %, based on the total weight of the at least two metals. In certain embodiments, the SCR catalyst is doped with W and Fe, wherein W is > about 25 wt. %, > about 50%, > about 75%, > 90 wt. %, or > 95 wt. %, based on the total weight of the Fe and W.

According to another aspect of the invention, provided is a system for treating a lean burn exhaust gas comprising (a) nitrogenous reducing agent injector; and (b) a dual function catalytic filter comprising (i) a soot filter having an inlet and an outlet, (ii) a soot oxidation zone on the inlet, wherein the soot oxidation zone comprises a soot oxidation catalytic component consisting essentially of at least one transition metal dispersed on a cerium and zirconium mixed and/or composite oxide, wherein the at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, and (iii) an SCR zone coated on the outlet, wherein the SCR zone comprises an SCR catalytic component, wherein said injector is disposed upstream of, and is in fluid communication with, said dual function catalytic filter. In certain preferred embodiments, the system further comprises a diesel oxidation catalyst disposed upstream of the injector, one or more flow-through SCR catalysts disposed downstream of the dual function catalytic filter, and an ammonia slip catalyst disposed downstream of the flow-through SCR catalyst(s). According to yet another aspect of the invention, provided is a method for treating a lean burn exhaust gas comprising (a) flowing a lean burn exhaust gas stream comprising soot, NOx, and a nitrogenous reducing agent through a dual function catalytic filter comprising (i) a soot filter having an inlet and an outlet, (ii) a soot oxidation zone on the inlet, wherein the soot oxidation zone comprises a soot oxidation catalytic component consisting essentially of at least one transition metal dispersed on a cerium and zirconium mixed and/or composite oxide, wherein the at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, and (iii) an SCR zone coated on the outlet, wherein the SCR zone comprises an SCR catalytic component; (b) oxidizing at least a portion of the soot at the soot oxidation zone; and (c) reducing at least a portion of said NOx at the SCR catalyst zone.

In another embodiment of the invention, the CSF and SCR functions on the filter will be performed by the same washcoat formulation. In this embodiment, the multifunctional catalyst component is coated on diesel particulate filters and will allow the coated filter to act both as a NH ₃ SCR catalyst and promote the combustion of soot by lowering the temperature for the ignition of the C-0 ₂ reaction.

BRI EF DESCRI PTION OF TH E DRAWINGS

Figure 1 is a diagram of a soot filter according to an embodiment of the present invention, the filter having an inlet coated with a soot oxidation catalyst zone and an outlet coated with an SCR catalyst zone;

Figure 2 is a diagram of a wall-flow soot filter according to an embodiment of the present invention, the filter having an inlet coated with a soot oxidation catalyst zone and an outlet coated with an SCR catalyst zone;

Figure 3 is a diagram showing a system with a configuration of components according to an

embodiment of the present invention;

Figure 4 is a graph depicting soot oxidation performance of an embodiment of the invention;

Figure 5 is a graph depicting NO _x conversion performance of an embodiment of the invention;

Figure 6 is a graph depicting NO _x conversion performance of an embodiment of the invention;

Figure 7 is a graph depicting back pressure performance of an embodiment of the invention;

Figure 8 is a graph depicting SCR performance of certain embodiments of the invention; and Figure 9 is a graph depicting NO _x conversion performance of an embodiment of the invention.

DETAILED DESCRI PTION OF PREFERRED EMBODIMENTS OF THE INVENTION

In certain embodiments, the invention is directed to a dual purpose catalytic filter that is capable of removing soot and NO _x from a lean burn exhaust gas. Turning to Figure 1 , shown is an embodiment of the invention comprising a soot filter 1 0, such as a diesel particular filter, having an inlet 14 and an outlet 15 relative to the direction of exhaust gas flow 13 through the filter. The filter inlet comprises a soot oxidation zone 14, while the filter outlet comprises an SCR zone 15. As used herein, the term "zone" means a distinct catalytic area within and/or on the filter substrate. For example, a zone can be an area of the filter substrate in which a catalyst has permeated or a catalyst layer residing on top of and/or within filter 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 filter 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 filter 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 filter 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).

Figure 2 shows a wall-flow filter 20 having inlet channels 23 and outlet channels 24 which are defined by a gas permeable walls 27 and gas impermeable inlet caps 25 and outlet caps 26. Exhaust gas having a direction of flow 29 enters the filter 20 via one or more of the inlet channels 23, passes through the gas permeable walls 27 which separate the inlet and outlet channels, and then exits the filter via the outlet channels 24. The exhaust gas entering the inlet channels typically comprises soot, NO _x , and preferably also contains a nitrogenous reducing agent, such as NH ₃ , which is used to convert the NO _x 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. The soot oxidation zone facilitates a low-temperature oxidation reaction wherein solid, carbonaceous particles of the soot are converted into gases, such as C0 ₂ and water vapor, which then pass through the gas permeable filter wall. As the exhaust gas passes through the SCR catalyst zone, at least a portion of the NO _x reacts with NH ₃ in the presence of the SCR catalyst, wherein the NO _x is reduced to N ₂ and other gases.

The respective orientation of the soot oxidation zone and the SCR zone are not particularly limited provided that a majority of the targeted particulate matter contacts the soot oxidation zone in a manner sufficient for soot combustion. Thus, in certain embodiments the two zones partially or completely overlap. In other 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 soot oxidation zone and the SCR zone permeate into opposite sides of the wall of a wall-flow filter. That is, the soot oxidation zone is created via the soot oxidation catalyst permeating into the wall from the inlet channel side of the wall and the SCR zone is created via the SCR catalyst permeating into the wall from the outlet channel side of the wall.

In certain preferred embodiments, the soot oxidation catalyst component comprises at least one transition metal dispersed on a mixed oxide or composite oxide or a mixture thereof as support material consisting of cerium and zirconium; or cerium oxide and zirconium oxide as single oxides or a composite oxide thereof or a mixture of the single oxides and the composite oxide dispersed on an inert oxide support material, whereon is dispersed at least one transition metal. Preferably, the content of cerium and zirconium as oxides (Ce0 ₂ -Zr0 ₂ ) in the catalyst is Ce _x Zr ₁ . _x 0 _2i wherein x is about 0.01 to about 0.90. Preferably, x is < 0.5, e.g., from about 0.1 to about 0.49, or from about 0.1 to about 0.4, or from about 0.1 to about 0.2.

The mixed oxides can be mixed oxides in solid solutions. "Composite oxide" as defined herein means a largely amorphous oxide material comprising oxides of at least two elements which are not true mixed oxides consisting of the at least two elements.

The one or more transition metals can be selected from the group consisting of a Group VIB metal, a Group IB metal, a Group IVA metal, a Group VB metal, a Group VIIB metal, a Group VI II metal, a rare earth metal and mixtures of any two or more thereof. The transition metal component can be present in the form of the oxide, hydroxide or free metal (i.e., zero valence). The Group VI I I metal can be any one or more of Ni, Co and Fe; illustrative examples of the Group IVA metals with utility in the present invention are Sn and Pb; the Group VB metals include Sb and Bi; one or more of Mn, Tc and Re can be used as the Group VI IB metal; rare earth metals include Ce; Group IB metals can include Cu; and one or more of Cr, Mo and W can be used for the Group VIB metal. Group VI I I noble metals are not preferred, not only because they are more expensive than base metals, but because they undesirably promote non-selective reactions such as: 4NH ₃ + 50 ₂ — > 4NO + 6H ₂ 0. Preferred transition metals are selected from the group consisting of Cr, Ce, Mn, Fe, Co, Ni, W and Cu, with Fe, W, Ce and Cu being more preferred, and Fe and W being particularly preferred.

In another embodiment, the base metal catalyst consists of two or more transition metals. In a preferred embodiment, the transition metal components of the base metal catalyst consist of iron and tungsten. An issue with ceria-based catalysts is that they can be deactivated by sulfur. However, binary combinations of transition metals including tungsten, such as tungsten and iron, improves the sulfur tolerance of the non-tungsten transition metal in the combination, in this case the Fe.

The total transition metal concentration present in the catalyst can be from about 0.01 to about 50 wt%, e.g. from about 0.1 to about 30 wt%, from about 0.5 to about 20 wt%, from about 1 to about 10 wt%, from about 5 to about 15 wt. %, or from about 2 to about 5 wt % based on the total weight of the catalyst.

The total amount of soot oxidation catalyst component in the soot oxidation zone will depend on the particular application, but could comprise about 0.1 to about 15 g/in ³ , about 1 to about 7 g/in ³ , about 1 to about 5 g/in ³ , about 2 to about 4 g/in ³ , or about 3 to about 5 g/in ³ of the soot oxidation catalyst component.

In certain embodiments, the soot oxidation catalyst component is supported on an inert oxide support selected from the group consisting of alumina, titania, non-zeolite silica-alumina, ceria, zirconia and mixtures, composite oxides and mixed oxides of any two or more thereof.

The soot oxidation catalyst composition can be applied to the filter substrate as an aqueous solution or as a washcoat slurry. Preferred washcoat loading for the soot oxidation catalyst is from about 0.1 to about 0.5 g/in ³ .

Catalysts for use in the method according to the invention are obtainable by methods known to the person skilled in the art including impregnation of support materials with aqueous transition metal salts, incipient wetness or co-precipitation. For example, the soot oxidation catalyst component can be obtained by co-precipitating salts of tungsten, cerium and zirconium. In a further embodiment, the catalyst is obtained by co-precipitating cerium and zirconium salts, then impregnating the resulting product only with a tungsten salt and calcining at temperatures between <600 °C. Whichever preparatory route is selected, it is desirable to activate the catalyst by heating in an existing environment, e.g. in air, to elevated temperatures for an appropriate period, e.g. at >600 °C such as at 650 °C and above or at 700 and above. This heat activation step is particularly desirable for a catalyst consisting of iron and tungsten dispersed on zirconia.

The SCR catalyst for use on the diesel particulate filter is not particularly limited. Preferred SCR catalyst compositions include a catalyst support material and a metal. Examples of suitable catalyst support materials include alumina, aluminosilicates such as zeolites, silicoaluminophosphate, aluminophosphates, or other molecular sieve, or a mixed phase molecular sieve such as AEI/CHA, AEI/SAV, AEN/U EI, AFS/BPH, BEC/ISV, ITE/RTH, KFI/SAV, IMTT/TON, SBS/SBT, and SSF/STF, titania, ceria, zirconia, vanadate, lanthana, or mixed oxide base materials. Particularly preferred support materials include aluminosilicate and aluminophosphate molecular sieves having a CHA, LEV, ERI, AEI, UFI, or DDR framework. Examples of suitable metals include Cu, Pb, Ni, Zn, Fe, Sb, W, Ce, Mo, Tn, Mg, Co, Bi, Cd, Ti, Zr, Sb, Mg, Cr, V, Ni, Ga, Ru, Rh, Pd, Ag, In, Sn, Re, Ir, Pt, and mixtures thereof, dispersed with the catalyst support material. In certain embodiments, preferred metals include vanadium (V), tungsten (W), iron (Fe), and copper (Cu), and mixtures thereof. In some embodiments, preferred SCR catalysts include copper loaded small pore molecular sieves such as chabazites having extra-framework (e.g., ion-exchanged) or free copper, including Cu:SSZ-13 and Cu:SAPO-34. Other useful SCR catalysts include Fe:Beta, Cu:ZSM5, and Cu:ZSM-34. In certain embodiments, Cu:CHA SCR catalysts are particularly preferred.

A particularly preferred SCR catalyst for the present invention is W-Ce0 ₂ -Zr0 ₂ or Fe-W- Ce0 ₂ -Zr0 ₂ . Applicants have found that modification of such catalyst will enable it to perform NH ₃ - SCR whilst lowering the ignition temperature of the C-0 ₂ reaction. In particular, it has been discovered that Ce _x Zr ₁ . _x 0 _2i wherein x is about 0.1 to about 0.99 is active for promoting the C-0 ₂ reaction, and by doping these materials with W their activities for the SCR reaction are enhanced. Accordingly, in certain embodiments, the invention pertains to W-Ce0 ₂ -Zr0 ₂ and/or Fe-W-Ce0 ₂ -Zr0 ₂ catalyst systems with the ability to perform both NO _x reduction reaction with NH ₃ and soot oxidation with 0 ₂ . The W, Fe, and Zr loadings on these materials can be optimized to achieve this dual functionality. Certain SCR catalyst compositions are typically applied to the filter as a washcoat slurry. Other SCR catalyst compositions can be applied to the filter as an aqueous solution.

The total amount of SCR catalyst component in the SCR zone will depend on the particular application, but could comprise about 0.1 to about 15 g/in ³ , about 1 to about 7 g/in ³ , about 1 to about 5 g/in ³ , about 2 to about 4 g/in ³ , or about 3 to about 5 g/in ³ of the SCR catalyst. Preferred washcoat loading for the SCR catalyst is from about 0.1 to about 0.5 g/in ³ .

In a preferred embodiment, the soot oxidation catalyst and SCR catalyst are present in a ratio of about 1 :25 to about 1 :2, e.g., from about 1 :1 0 to about 1 :5. In certain embodiments having such ratios of soot oxidation catalyst to SCR catalyst, the soot oxidation catalyst and SCR catalyst have the same or similar formulations. For example, the soot oxidation catalyst and SCR catalyst can both be either W-Ce0 ₂ -Zr0 ₂ and/or Fe-W-Ce0 ₂ -Zr0 ₂ , wherein the inlet side of the filter is coated with less catalyst composition compared to the outlet side of the filter. In certain other embodiments, the soot oxidation catalyst and the SCR catalyst have similar formulations except that the relative ratios of the W:Fe and/or Ce0 ₂ :Zr0 ₂ are different.

The soot catalyst and the SCR catalyst can include other, non-catalytic components such as carriers, binders, 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, etc. Accordingly, a catalyst zone comprising a catalytic component can also include additional, non- catalytic components as well. Examples of such optional, non-catalytic components can include non- doped alumina, titania, non-zeolite silica-alumina, ceria, and zirconia that are present in the catalyst composition, but serve one or more non-catalytic purposes.

The type of DPF substrate for use in the present invention is not particularly limited provided that the filter is a suitable substrate for a soot oxidation zone and SCR zone as described herein, and has suitable physical properties, such as porosity, mean pore size, etc., that are compatible with the soot oxidation and SCR zones. Suitable DPF can include nonwoven fibrous filters and metallic or cordierite honeycombs, as well as other types of diesel particulate filters. Preferred filter substrates for use in mobile application are monoliths having a so-called honeycomb geometry which comprises a plurality of adjacent, parallel channels, each channel typically having a square, round, hexagonal, or triangular cross-sectional. The honeycomb shape provides a large catalytic surface with minimal overall size and pressure drop. Other substrates include sheets or screens that can be zoned in any suitable fashion including, for example, stacking, rolling, or arraying about a central axis. Other substrates include packed beds which can be formed with pellets of the adsorbent, preferably held together with a binder or sintered to form a cohesive mass.

Soot filters for use in the present invention can be fabricated using a variety of materials including sintered metal, ceramic or metal fibers, etc. A preferred type of filter is a so-called "wall- flow" filter made from porous ceramic or other material in the form of a monolithic array of many small channels running substantially parallel over a majority of the length of the filter body, and wherein the channels are capped at alternate ends in a checkerboard fashion. Specific materials of construction for wall-flow monoliths include cordierite, a-alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate, ceramic composite fibers, or a porous refractory metal. Preferred materials include cordierite, silicon carbide, and alumina titanate.

Capping or plugging alternate ends of the channels of the wall-flow filter forces the exhaust gas through the porous ceramic channel walls. Although porous, these wall prevent most of the particulate from passing through. That is, exhaust gas untreated by the catalytic filter flows into the substrate channels (i.e., the filter inlet) where it contacts the upstream side of a substrate wall. During operation of an engine, a pressure differential exists between the inlet and outlet faces of the substrate (higher pressure at the inlet face relative to the outlet face), and thus a pressure differential also exists between the upstream side and downstream side of the substrate wall. This pressure differential, along with the gas permeable nature of the walls, allows the exhaust gas that flows into a channel which is open to the inlet face, to pass from the upstream side of a porous wall to the downstream side of that wall, and then into an adjacent channel (i.e., filter outlet) which is open to the downstream section of the exhaust system. Wall flow filters useful in the present invention have up to about 700 channels (cells) per square inch of cross section. In one embodiment, the wall-flow filter contains about 100 to 400, cells per square inch ("cpsi").

The actual shape and dimensions of the filter substrate, as well as properties such as channel wall thickness, its porosity, etc., depend on the particular application of interest. However, in certain embodiments, the average dimensions of the pores in the filter channel walls of the ceramic wall-flow filter through which the exhaust gas passes range from about 5 to about 50 μιη, for example about 15 to about 30 μιη. I n other embodiments, the mean pore size of the filter is about 1 0 to about 200 nm. ln certain embodiments, wall-flow filters have a porosity of about 30 to 40%. In other embodiments, the wall-flow filter has a porosity of at least 40% (e.g., from 45% to 75%) having a mean pore size of at least 5 microns (e.g., from 5 to 30 microns) and preferably at least 55% (e.g., from 55% to 75%).

Wall flow filters for use with the present invention preferably have an efficiency of least 70%, at least about 75%, at least about 80%, or at least about 90%. In certain embodiments, the efficiency will be from about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. 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 0.05 microns to 2.5 microns. Thus, the efficiency can be based on this range or a sub-range, such as 0.1 to 0.25 microns, 0.25 to 1 .25 microns, or 1 .25 to 2.5 microns. Preferred porosity for cordierite filters is from about 60 to about 75 %.

During normal operation of the exhaust system, the soot and other particulates accumulate on the upstream sides of the walls which lead to an increase in backpressure. To alleviate this increase in backpressure, the filter substrates are continuously or periodically regenerated by combusting the accumulated soot. The combustion process is promoted by the soot oxidation catalyst zone. Exhaust gas passing through the porous substrate walls also contacts the SCR catalyst embodied in the walls, thus eliminating a major portion of the NO _x components from the exhaust gas.

The soot oxidation zone and SCR zone can be incorporated into the soot filter by any practical means. For example, the inlet channels of a wall-flow soot filter can be dipped into an soot oxidation catalyst composition at a depth and for a period of time that will allow the soot oxidation catalyst composition to permeate the filter walls to a certain depth and/or concentration. Additional techniques, such as application of pressure or a vacuum, can be used to promote adequate, even, and/or more rapid permeation of a particular coating. After the soot oxidation catalyst composition permeates the inlet of the wall-flow filter, the filter is dried and then the outlet channels of the filter are dipped into an SCR catalyst composition at a depth and for a period of time that will allow the SCR catalyst composition to permeate the filter walls to a certain depth and/or concentration. Again, additional techniques, such as application of pressure or a vacuum, can be used to promote adequate, even, and/or more rapid permeation of a particular coating. The SCR zone is then dried. One or more of the dipping processes can be repeated to achieve the desired coating level. After acceptable catalyst loadings are obtained, the catalytic coating is activated, preferably at a temperature of about 1 00 ^e C to about 300 ^e C for about 1 to about 3 hours. The activated filter is calcined to remove additional moisture at a temperature of about 450 ^e C to about 550 ^e C for about 1 to about 3 hours. A preferred method of application is AI D. The drying and calcining steps are preferably performed as per standard CSF preparation conditions.

Another aspect of the invention is directed to a system for treating lean-burn exhaust gas. Such exhaust gas systems are configurations of two or more discrete devices or components, each of which are capable of modifying the composition of the exhaust gas independently of the other(s), but interact with the other(s) to form a coherent scheme for treating the exhaust gas. Preferably, one or more of the components of the exhaust gas system interact to produce a synergistic result.

In a preferred embodiment, the system of the present invention comprises a dual function catalytic soot filter as described herein in fluid communication with an injector or other device for introducing a nitrogenous reductant into the exhaust gas, wherein the injector or other device is disposed upstream of the filter. The inventors have discovered that the soot oxidation zone of the filter will not consume a nitrogen-based reductant (urea, ammonia, etc.) which is required for the downstream SCR reaction. Therefore, the present invention allows a reductant to be dosed into the exhaust gas upstream of the filter containing the soot oxidation catalyst. In certain embodiments, the system further comprises an exhaust gas stream generated by a lean burn internal combustion engine, one or more conduits for carrying a flowing exhaust gas, wherein the conduits are in fluid connection with at least some of the components of the exhaust system, and/or a source of nitrogenous reductant.

The injector can continuously, periodically, or intermittently introduce the reductant, such gaseous ammonia, ammonia in aqueous solution, aqueous urea, or ammonia from an ammonia generator, into the exhaust gas at a dose effective for optimization of the downstream SCR reaction. The injector is in fluid communication with the exhaust gas stream and may be attached, connected to, and/or integrated with a conduit, such as a pipe, for directing the exhaust through at least a portion of the exhaust gas system. The injector may also be in fluid communication with a reduction agent supply tank to provide for repeated injections of the reduction agent.

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 NO _x content of the exhaust gas. The metering of the nitrogenous reductant can be arranged such that 60% to 200% of theoretical ammonia is present in exhaust gas entering the SCR catalyst calculated at 1 :1 NH ₃ /NO and 4:3 NH ₃ /N0 ₂ . The control means can comprise a pre-programmed processor such as an electronic control unit (ECU). Controlling the metering involves limiting the introduction of the nitrogenous reductant into the flowing exhaust gas only when it is determined that the SCR catalyst is capable of catalyzing NO _x reduction at or above a desired efficiency, such as at above 1 00 ^e C, above 150 ^e C or above 1 75 ^e C. 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 certain preferred embodiments, the injector is disposed upstream of the dual function catalytic filter with no intervening SCR or other catalytic components between the injector and the filter. That is, the NH ₃ in the exhaust stream is not consumed or otherwise utilized after it enters the exhaust gas stream and prior to contacting the SCR zone of the filter.

In another embodiment, all or at least a portion of the nitrogen-based reductant, particularly NH ₃ , can be supplied by a NO _x adsorber catalyst (NAC), a lean NO _x trap (LNT), or a NO _x storage/reduction catalyst (NSRC), disposed upstream of the dual function catalytic filter. One of the functions of the NAC in the present invention is to provide a source of N H ₃ for the downstream SCR reaction. Accordingly, the NAC is configured in the system in a manner similar to that of the injector - i.e., upstream of the dual function catalytic filter and preferably with no intervening SCR or other catalytic components between the NAC and the filter. NAC components useful in the present invention 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 10 to about 200 g/ft ³ , such as 20 to 60 g/ft ³ . Alternatively, the precious metal of the catalyst is characterized by the average concentration which may be from about 40 to about 1 00 grams/ft ³ .

Under certain conditions, during the periodically rich regeneration events, NH ₃ may be generated over a NO _x adsorber catalyst. The SCR catalyst downstream of the NO _x adsorber catalyst may improve the overall system NO _x reduction efficiency. In the combined system, the SCR catalyst is capable of storing the released N H ₃ from the NAC catalyst during rich regeneration events and utilizes the stored NH ₃ to selectively reduce some or all of the NO _x that slips through the NAC catalyst during the normal lean operation conditions.

In certain embodiments, the system further comprises a diesel oxidation catalyst (DOC) to oxidize hydrocarbon based soluble organic fraction (SOF) and carbon monoxide content of diesel exhaust by simple oxidation:

CO + ½o ₂ → co ₂

[HC] + 0 ₂ → C0 ₂ + H ₂ 0

The DOC may also serve to oxidize NO into N0 ₂ , which in turn, may be used to oxidize particulate matter in particulate filter. Additionally, the DOC may serve to reduce the particulate matter (PM) in the exhaust gas.

Preferably, the DOC is disposed upstream of the upstream of the dual function catalytic filter, and more preferably upstream of the SCR reductant injector or NAC.

In a further embodiment, an 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 zeolite catalyst having a ratio of NO to N0 ₂ of from about 4:1 to about 1 :3 by volume, e.g. at an exhaust gas temperature at oxidation catalyst inlet of 250 ^e C to 450 ^e C. In another embodiment, the system further comprises a Closed Coupled Catalyst (CCC) upstream of the DOC.

The oxidation catalyst can include at least one platinum group metal (or some combination of these), such as platinum, palladium, or rhodium, coated on a flow-through monolith substrate. Other metal catalysts that can be used in the DOC include aluminum, barium, cerium, alkali metals, alkaline- earth metals, rare-earth metals, or any combinations thereof. In one embodiment, the at least one platinum group metal is platinum, palladium or a combination of both platinum and palladium. The platinum group metal can be supported on a high surface area washcoat component such as alumina, a zeolite such as an aluminosilicate zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titania or a mixed or composite oxide containing both ceria and zirconia. In a preferred embodiment, the diesel oxidation catalyst composition contains about 1 0 to 120 g/ft ³ of a platinum group metal (e.g., platinum, palladium or rhodium) dispersed on a high surface area, refractory oxide support (e.g., γ-alumina).

In certain embodiments, one or more additional SCR catalyst components can be included in the system, preferably downstream of the dual function catalytic filter, to further reduce the concentration of NO _x in the exhaust gas. For example, upon exiting the dual function catalytic filter, the exhaust gas passes through a flow-through substrate coated with an SCR catalyst. Thus, the flow- through SCR catalyst is disposed downstream of the dual function catalytic filter. The NO _x concentration of the exhaust gas is reduced as the gas passes through the dual function catalytic filter and then is further reduced as the gas sequentially passes through the one or more SCR flow-through substrates. In another embodiment, the system further comprises an additional reductant injector upstream of the SCR flow-through catalyst and downstream of the dual function catalytic filter. In certain embodiments, the one or more downstream SCR flow-through catalysts are extruded articles.

The number of additional SCR catalyst flow-through components can be of any practical number, such as 1 , 2, 3, or 4. The downstream SCR catalyst(s) may be the same or different from the SCR catalyst coated on the dual function catalytic filter. In certain embodiments, preferred SCR catalysts include copper loaded small pore molecular sieves such as chabazites having extra- framework or free copper, including Cu:SSZ-13 and Cu:SAPO-34.

In certain embodiments, the system further comprises an ammonia slip catalyst disposed downstream of the dual function catalytic filter, and in some embodiments, downstream of the flow- through SCR components. The ASC serves 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. Thus, the ASC reduces the concentration of ammonia slip from the SCR reaction, the release of ammonia from the catalyst surface during rapid temperature increases, or from the use of a stoichiometric excess of reductant. Preferably, the ASC material should be selected to favor the oxidation of ammonia instead of the formation of NO _x or N ₂ 0. Preferred catalyst materials include platinum, palladium, or a combination thereof, with platinum or a platinum/palladium combination being preferred. Preferably, the catalyst is disposed on a high surface area support, including but not limited to alumina. In certain embodiments, the ASC is applied to a substrate, preferably substrates that are designed to provide large contact surface with minimal backpressure, such as flow-through metallic or cordierite honeycombs. For example, a preferred substrate has between about 25 and about 300 cells per square inch (CPSI) to ensure low backpressure. Achieving low backpressure is particularly important to minimize the ASC's effect on the low-pressure EGR performance. The ASC can be applied to the substrate as a washcoat, preferably to achieve a loading of about 0.3 to 2.3 g/in ³ . To provide further NO _x conversion, the front part of the substrate can be coated with just SCR coating, and the rear coated with SCR and an NH ₃ oxidation catalyst such as Pt or Pt/Pd on an alumina support.

Another aspect of the invention relates to a method whereby nitrogen oxides are reduced with a nitrogenous reducing agent, preferably at a temperature of at least 1 00 °C, such as from about 150 °C to 750 °C. In certain embodiments, the method comprises the steps of flowing a lean burn exhaust gas containing soot, NO _x , and a nitrogenous reducing agent, preferably N H ₃ , through a dual function catalytic filter of the present invention wherein the exhaust gas exiting the filter has a reduced concentration of soot and NO _x compared to the exhaust gas flowing into the filter. The method may further comprise one or more of the following steps: (a) accumulating and/or combusting soot that is in contact with the inlet of the dual function catalytic filter; (b) introducing a nitrogenous reducing agent into the exhaust gas stream prior to contacting the dual function catalytic filter, preferably with no intervening catalytic steps involving the treatment of NO _x and the reductant; (c) generating NH ₃ over a NO _x adsorber catalyst, and preferably using such NH ₃ as a reductant in a downstream SCR reaction; (d) contacting the exhaust gas stream with a DOC to oxidize hydrocarbon based soluble organic fraction (SOF) and/or carbon monoxide into C0 ₂ , and/or oxidize NO into N0 ₂ , 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 further reduce the NOx concentration in the exhaust gas, wherein the one or more flow-through SCR catalyst device(s) are preferably disposed downstream of the dual function catalytic filter; and (f) contacting the exhaust gas with an ammonia slip catalyst, preferably downstream of the dual function catalytic filter and, if present, the one or more flow-through SCR catalyst devices 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. ln a particular embodiment, the temperature range for the SCR reaction is from 1 75 to 550 ^e C. In another embodiment, the temperature range is from 1 75 to 400 ^e C. In yet another embodiment, the temperature range is 450 to 900 ^e C, preferably 500 to 750 ^e C, 500 to 650 ^e C, 450 to 550 ^e C, or 650 to 850 ^e C. In a particular embodiment, the nitrogen oxides reduction is performed in the presence of oxygen. In the method according to the invention, the addition of nitrogenous reductant can be controlled so that NH ₃ at the catalyst inlet is controlled to be 60% to 200% of theoretical ammonia calculated at 1 :1 NH ₃ /NO and 4:3 NH ₃ /N0 ₂ . In certain embodiments, the ratio of nitrogen monoxide to nitrogen dioxide in the catalyst inlet gas is from 4:1 to 1 :3 by volume. In this regard, the ratio of nitrogen monoxide to nitrogen dioxide in the gas can be adjusted by oxidizing nitrogen monoxide to nitrogen dioxide using an oxidation catalyst located upstream of the catalyst.

The nitrogenous reducing agent can be derived from any suitable source including ammonia per se, hydrazine or an ammonia precursor selected from the group consisting of urea ((N H ₂ ) ₂ CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate and ammonium formate. NH ₃ can also be supplied by a lean NOx trap or similar device disposed upstream of the dual function filter.

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. 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.

EXAMPLES

The following non-limiting examples are provided to further demonstrate particular aspect of certain embodiments of the invention. Example 1 :

Physical mixtures of simulated diesel exhaust gas soot and compositions of cordierite, Ce0 ₂ -Zr0 ₂ , W- Ce0 ₂ -Zr0 ₂ (5 wt. % W), W-Ce0 ₂ -Zr0 ₂ (15 wt. % W), were prepared as powders. These powders were tested in a TPO type experiment whereby the mixture is ramped in a gas mixture containing He and 5% 0 ₂ . The soot ignition temperature is measured by the C0 ₂ formation. The results of these tests are provide in Figure 4. In particular, the Ce _x Zr ^ 0 ₂ (x=1 .0) promotes the oxidation of soot and the ignition temperature is decreased from a temperater of about 600 ^e C in absence of the catalyst to a temperature of about 450 ^e C. The presence of W lowers the reactivity slightly.

Example 2:

Compositions of Ce0 ₂ -Zr0 ₂ , W-Ce0 ₂ -Zr0 ₂ (5 wt. % W), W-Ce0 ₂ -Zr0 ₂ (15 wt. % W), were prepared as powders. These powders were tested in a microreactor to determine the effect of tungsten on the NO _x reduction activity of Ce0 ₂ -Zr0 ₂ . The results of these tests are provide in Figure 5. As the results show, the presence of W enhances the NO _x reduction activity of Ce0 ₂ -Zr0 ₂ .

Example 3:

Compositions of W-Ce0 ₂ -Zr0 ₂ and W-Ce0 ₂ were prepared as powders. These powders were tested in a microreactor to determine the effect of Zr0 ₂ on NO _x reduction activity. The results of these tests are provided in Figure 6. As the results show, a W- Ce0 ₂ catalyst is effective for NO _x reduction.

Example 4:

Compositions of Ce0 ₂ -Zr0 ₂ and W-Ce0 ₂ -Zr0 ₂ were coated on separate SiC flow through filter cores (1 inch diameter and 7 inch long ) at a loading of about 0.3g per cubic inch. The soot oxidation activities of these coated filters were measured by first loading them with soot produced during combustion of US 06 Diesel fuel. The filter was loaded to about 1 0-20 mg soot per cu inch. The soot oxidation experiment was done in a gas mixture of N ₂ with 10% 0 ₂ at a GHSV ~ 60K hr ^"1 monitoring the back pressure. The bare filter containing no catalyst and without any soot show an increase in back pressure with increasing temperature due to changes in kinetic energy of the gas. The bare filter loaded with soot showed a higher initial back pressure to the clean filter and then a drop in back pressure at a temperature of about 550 ^e C caused by the oxidation of the soot. This drop in back pressure occurs at a lower temperature on the filter coated with the Ce0 ₂ -Zr0 ₂ and W- Ce0 ₂ -Zr0 ₂ catalyst due to their promotion of the soot combustion process. The results of this example are shown in Figure 7.

Example 5:

The cores prepare in Example 4 were measured for their NH ₃ SCR activities. The coated filter catalyst was measured in a gas mixture containing 500ppm NO, 500ppm NH ₃ , 5% C0 ₂ , 5% H ₂ 0, 10% 0 ₂ and 300ppm CO. Although the Ce0 ₂ -Zr0 ₂ was inactive and unselective for reacting NOX with NH ₃ , the W- Ce0 ₂ -Zr0 ₂ catalyst shows high reactivity for the NH ₃ -SCR reaction. The results of this example are shown in Figure 8.