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    • 专利摘要:
    ARTICLE AND METHOD TO TREAT AN EXHAUST GAS, AND, SYSTEM TO TREAT NOX IN A POOR BURNING EXHAUST GASA dual function catalytic filter is provided having a soot filter with an inlet and an outlet, a soot oxidation layer at the inlet, wherein the soot oxidation layer comprises a soot oxidation catalytic component consisting essentially of at least least one transition metal dispersed in mixed cerium and zirconium oxide and / or composite, where at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu , and combinations thereof, and a coated SCR layer at the outlet, wherein the SCR layer comprises a SCR catalytic component. Also provided are methods for removing NOx and soot from a poorly burning exhaust gas using the dual-function catalytic filter.
    公开号:BR112013030719A2
    申请号:R112013030719-6
    申请日:2012-05-31
    公开日:2020-07-21
    发明作者:Glen Spreitzer；Sougato Chatterjee；Raj Rao Rajaram；Jillian Elaine Collier；Paul James Millington；Sylvie Cécile Laroze
    申请人:Johnson Matthey Public Limited Company；
    IPC主号:
    专利说明:

    “ARTICLE AND METHOD FOR TREATING EXHAUST GAS, AND, SYSTEM TO TREAT NOX IN POOR BURNING EXHAUST GAS ”
    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 the combustion of hydrocarbon fuel, particularly a soot-poor exhaust gas containing nitrogen oxides produced - by a diesel engine.
    B) Description of the Related Art: The exhaust gas is generated during the combustion of fuels such as natural gas, gasoline, diesel fuel, fuel oil or coal. When combustion takes place in a chamber such as an engine or furnace, the resulting exhaust gas is typically treated before being discharged into the atmosphere through an exhaust pipe, exhaust flue or the like. The largest portion of exhaust gas consists of nitrogen (N>), water vapor (H7, O), and carbon dioxide (CO); but the untreated exhaust gas also contains, in relatively small parts, - undesirable harmful and / or toxic substances, such as incomplete combustion carbon monoxide (CO), unburned fuel hydrocarbons (HC), nitrogen oxides (NOx ) (eg nitric oxide (NO), nitrogen dioxide (NO), and nitrous oxide (N7O0)) from excessive combustion temperatures, and particulate matter (insoluble carbon soot particles, liquid hydrocarbons (eg lubricating oil and unburned oil), and a soluble organic fraction Of particular relevance to the present invention is the exhaust gas emitted from diesel engines that typically operate using a high air-to-fuel ratio (ie, very poor conditions). Such poor burning conditions often result in an exhaust gas with relatively high emissions of particulate matter and NO, - two components that have proved difficult to convert effectively into more substances. benign.
    Diesel engines are often equipped with exhaust systems that include one or more catalytic components that work separately or in combination to treat the exhaust gas before it is released into the atmosphere. For example, it is known that NO can be converted to elemental nitrogen, N ,, and water, with NO reacting in the exhaust gas with NH; in the presence of some catalysts supported through a process commonly referred to as selective catalytic reduction (SCR). Known SCR catalysts include vanadium (V2Os) loaded by a mixture of ceria (CeO;) and alumina (Al2O3) on a support (see, EP O 246 859), or V; Os / WO; supported on TiO; (see WO 99/39809). Other SCR catalysts have also been proposed such as mixed metal oxides such as Fe-W / CeZrO, (WO 2009/001131) and molecular sieves of aluminosilicate and silicoaluminophosphate loaded with an extra structure metal such as Cu: SAPO-34 (US 2010 / 0290963). Unlike treatment with NO, soot remediation in an exhaust gas typically involves mechanical filtration. For example, soot emissions can be reduced by passing an exhaust gas containing soot through a diesel particulate filter (DPF), such as a cordierite water flow filter (US 2010/0170230). However, the accumulation of soot particles on or in the filter can cause an undesirable increase in back pressure through the filter which typically leads to decreased efficiency and - engine performance. To regenerate the filter, the accumulated carbon-based soot must be removed from the filter, which is typically done by periodically subjecting soot to combustion. Such a combustion technique involves the catalytic oxidation of soot at low temperatures by means of a soot oxidation catalyst incorporated in the filter (ie, a catalytic soot filter (CSFP)). (US
    4,902,487). Conventional exhaust systems comprise separating components for the treatment of NO, (SCR) and soot treatment (CSFP). —It is still often desired to design individual exhaust components to perform more than one function in order to reduce the total space required for 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 a substrate to serve two functions, namely catalytic conversion of NO, by the catalyst of SCR and soot removal by the filter. For example, US Patent Publication 2010/0180580 discloses that an SCR catalyst can be applied to a wall flow DPF. However, removing the soot oxidation catalyst in an SCRF requires that the soot accumulated on the filter surface be burned at very high temperatures. Very high temperature SCR catalysts, such as Cu: SAPO-34, are available but are insoluble in water and therefore, these catalysts should be applied to the filter as a viscous coating layer. Coating the filter with a thick catalytic slurry causes a significant increase in back pressure and a corresponding reduction in fuel economy and engine power. In addition, a combination of conventional SCR and oxidation catalysts is not possible, as it results in localized competition for NO, thereby reducing the conversion efficiency of the SCR catalyst.
    Therefore, the need remains for an effective system to treat soot and NOx in a poorly burning exhaust gas. This invention satisfies this need, among others.
    SUMMARY OF THE INVENTION The present inventors have discovered a dual-function catalytic filter which, in some embodiments, has a soot-burning catalyst at the filter inlet and an SCR catalyst at the filter outlet. By coating a filter substrate with a soot oxidation catalyst capable of burning particulates in the inlet channels and an SCR coating layer in the outlet channels, the complexity, size, and cost of a gas treatment system exhaust can be reduced. In addition, the present inventors have found that some soot oxidation catalysts will not consume reducers based on nitrogen, urea, ammonia, etc. that are needed for the SCR reaction downstream. Therefore, the present invention allows a reducer to be dosed in the exhaust gas upstream of the filter containing the soot oxidation catalyst. In addition, in some embodiments, the separation of the soot oxidation catalyst and the SCR catalyst will prevent localized competition for NO; and improves overall activity. Other advantages of the invention include less backpressure and better overall emission and engine performance compared to conventional systems using separate catalyzed soot filters or SCR catalysts loaded on the filter without a soot oxidation catalyst. In this way, such systems can be used to satisfy stricter emission requirements that can be imposed by regulatory agencies.
    Further performance improvements can be achieved by integrating the dual-function catalytic filter with an upstream diesel oxidation catalyst and at least one SCR direct flow catalyst downstream followed by an ammonia release catalyst. In this way, in some 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 one ammonia release catalyst downstream.
    Therefore, an article is provided to treat an exhaust gas comprising (a) a soot filter having an inlet and an outlet; (b) a soot oxidation inlet zone, wherein the soot oxidation zone comprises a catalytic soot oxidation component which essentially consists of at least one transition metal dispersed in a mixed cerium and zirconia oxide and / or composite, in which at least one transition metal is selected from the group consisting of a metal from Group VIB, a metal from Group IB, a metal from Group IVA, a metal from Group VB, a metal from Group VIIB, a metal Group VIII metal, and combinations thereof; and (c) an SCR zone at the outlet, wherein the SCR zone comprises a catalytic SCR component.
    The inventors found that soot oxidation activity generally increases with the relative concentration of ZrO, for CeO; increases. In some preferred embodiments, the soot oxidation catalyst component has a formula M: Ce, O>, 7Zr1-.x, 02, where 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 of these, with W being more preferred. In some 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 some embodiments, x <about O, 1, such as <about 0.07, <about 0.05, <about 0.03, or <about 0.01, as long as x is> 0.001 or> about 0.005. Some SCR catalyst components have a formula of M: CexO0,3Z1-, 02, where x = about 0.1 to about 1.0, with x —when> about 0.3 is preferred, x> about 0.5 being more preferred, eg> about 0.7 being even more preferred; and M is selected from W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations of these, with Fe and W being more preferred. For embodiments that include W in the SCR catalyst, the inventors have found that SCR activity increases with increasing CeO concentration, increases with increasing W concentration, and particularly that SCR activity increases with combination of increased CeO concentration; and increased W concentration.
    In some embodiments, the value of x for the SCR catalyst is> about 0.9, such as 0.95, 0.99, or 1.00. In some preferred embodiments, the SCR catalyst is doped with at least two metals, W> about 25% by weight,> about 50%,> about 75%,> 90% by weight, or> 95% by weight, based on the total weight of the at least two metals.
    In some embodiments, the SCR catalyst is doped with W and Fe, where W is> about 25% by weight,> about 50%,> about 75%,> 90
    % by weight, or> 95% by weight, based on the total weight of Fe and W.
    In accordance with another aspect of the invention, a system is provided for treating a low-burning exhaust gas comprising (a) nitrogen reducing agent injector; and (b) a dual-function catalytic filter comprising (1) a soot filter having an inlet and an outlet, (11) a soot oxidation inlet zone, wherein the soot oxidation zone comprises a catalytic component of soot oxidation consisting essentially of at least one transition metal dispersed in mixed cerium and zirconia oxide and / or composite, in —which at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn , Fe, Co, Ni, Cu, and combinations thereof, and (111) an SCR zone at the outlet, in which the SCR zone comprises a SCR catalytic component, in which said injector is arranged upstream of, and is in fluid communication with, said dual-function catalytic filter.
    In some preferred embodiments, the system also comprises a diesel oxidation catalyst disposed upstream of the injector, one or more direct flow SCR catalysts disposed downstream of the dual-function catalytic filter, and an ammonia release catalyst disposed downstream of the direct flow SCR catalyst (s).
    In accordance with yet another aspect of the invention, a method is provided for treating a low-burning exhaust gas comprising (a) flowing a low-burning exhaust gas stream comprising soot, NOx, and a nitrogen reducing agent through of a dual-function catalytic filter comprising (1) a soot filter having an inlet and an outlet, (ii) a zone at the soot oxidation inlet, wherein the soot oxidation zone comprises a catalytic oxidation component of soot consisting essentially of at least one transition metal dispersed in a mixed cerium and zirconia oxide and / or —compound, in which at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, and (li) an SCR zone at the outlet, wherein the SCR zone comprises a catalytic SCR component; (b) oxidizing at least a portion of the soot in the soot oxidation zone; and (c) reducing at least a portion of said 15 "NOx in the SCR catalyst zone. In another embodiment of the invention, the functions of CSF and SCR in the filter will be performed by the same coating layer formulation. In this embodiment, the multifunctional catalyst component is coated on diesel particulate filters and will allow the coated fabric to act as both an NHS SCR catalyst and promoting soot combustion by lowering the temperature for ignition of the CO reaction.
    BRIEF DESCRIPTION OF THE FIGURES The Figure | it is a diagram of a soot filter according to - in one embodiment of the present invention, the filter having an inlet lined with a soot oxidation catalyst zone and an outlet lined 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 lined with a soot oxidation catalyst zone and an outlet lined with a catalyst zone SCR; 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 the soot oxidation performance of an embodiment of the invention; Figure 5 is a graph depicting the NO conversion performance of an embodiment of the invention; Figure 6 is a graph depicting the NO conversion performance of an embodiment of the invention; Figure 7 is a graph that represents the backpressure performance of an embodiment of the invention; Figure 8 is a graph representing the SCR performance of some embodiments of the invention; and Figure 9 is a graph depicting the NO conversion performance of an embodiment of the invention. DETAILED DESCRIPTION OF METHODS
    PREFERRED PROCEDURES OF THE INVENTION In some embodiments, the invention relates to a dual purpose catalytic filter that is capable of removing soot and NO from a poorly burning exhaust gas. Returning to Figure 1, an embodiment of the invention is presented which comprises a soot filter 10, such as a particular diesel filter, having an inlet 14 and an outlet 15 with respect to the direction of the flow of the exhaust gas 13 through the filter. The filter inlet comprises a soot oxidation zone 14, while the filter outlet comprises a 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 that resides on top of and / or within the filter substrate.
    The zone can be a discrete area, completely separate from other zones, it can be adjacent to, or overlap with, other zones, or partially merged into other zones.
    The term "inlet" means the side, front, surface, channel, and / or portion of the filter on which an exhaust gas typically flows from an external source.
    The term "outlet" means the side, front, surface, channel, and / or portion of the filter from which an exhaust gas typically exits the filter.
    The phrases “at the entrance” and “at the exit”, with respect to the orientation of a catalytic zone and a filter substrate, are intended to include a catalyst that resides as a zone or layer at the top of the front of the substrate and / or within the walls of the substrate
    (ie, 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 gas-permeable walls 27 and gas-impermeable inlet caps 25 and outlet caps 26. The exhaust gas having a flow direction 29 enters the filter 20 via one or more of the inlet channels 23, passes through the gas-permeable walls 27 that separate the inlet and outlet channels, and then leaves the filter via the outlet channels 24. The gas Exhaust gases entering the inlet channels typically comprise soot, NO ,, and preferably also contain a nitrogen reducing agent, such as NH ;, which is used to convert NO into other gases through 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 entrance where it communicates the soot oxidation zone.
    The fuliszem oxidation zone facilitates a temperature oxidation reaction in which the solid carbonaceous soot particles are converted into gases, such as CO, 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 reacts with NH; in the presence of the SCR catalyst, where NO is reduced to N, and other gases. The respective orientation of the soot oxidation zone and the —SCR zone are not particularly limited as long as a majority of the targeted particulate matter comes into contact with the soot oxidation zone in a manner sufficient for soot combustion. Thus, in some embodiments, the two zones overlap partially or completely. In other embodiments, the two zones converge between entry and exit, while in other embodiments these are spatially separated. Inlet and outlet zones can exist as a coating on the surface of the filter substrate or can diffuse or permeate all or a portion of the filter substrate. In a particularly preferred embodiment, the soot oxidation zone and the SCR zone are permeated on the opposite sides of the wall from a wall flow filter. That is, the soot oxidation zone is created by means of the soot oxidation catalyst permeating the wall on the side of the inlet channel and the SCR zone is created by means of the SCR catalyst permeating on the wall on the channel side exit from the wall.
    In some preferred embodiments, the soot oxidation catalyst component comprises at least one transition metal dispersed in a mixed oxide or composite oxide or a mixture thereof as a support material consisting of cerium and zirconium; or cerium oxide and zirconium oxide as single oxides or a composite oxide of these or a mixture of single oxides and composite oxide dispersed in an inert oxide support material, in which at least one metal of transition. Preferably, the content of cerium and zirconium as oxides (CeO; -ZrO> ») in the catalyst is CexZr1-2, where x is about 0.01 to about 0.90. Preferably, x is <0.5, for example, 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.
    Mixed oxides can be mixed oxide in solid solutions. "Composite oxide" as defined herein means a widely amorphous oxide material that comprises oxides of at least two elements that are not true mixed oxides that consist of at least two elements.
    The one or more transition metals can be selected from the group consisting of a metal from the VIB Group, a metal from the IB Group, a - metal from the IVA Group, a metal from the VB Group, a metal from the VIIB Group, a metal from the Group VIII, a rare earth metal and mixtures of any two or more of these. The transition metal component can be present in the form of oxide, hydroxide or free metal (i.e., zero valence). The Group VIII metal can be any one or more of Ni, Co and Fe; illustrative examples of Group IVA metal useful in the present invention are Sn and Pb; Group VB's metal includes Sb and Bi; one or more of Mn, Tc and Re can be used as the Group VIIB metal; rare earth metals include Ce; Group IB metals may include Cu; and one or more of Cr, Mo and W can be used for the VIB Group metal. Noble metals in Group VII are not preferred, not only because they are more expensive than base metals, but because they undesirably promote non-selective reactions such as: 4NH; + 50; > 4NO + 6H, 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. A problem with cerium-based catalysts is that they can be deactivated by sulfur. However, binary combinations of transition metals including tungsten, such as tungsten and iron, improve the sulfur tolerance of the transition metal other than tungsten in the combination, in this case Fe.
    The concentration of total transition metal present in the catalyst can be from about 0.01 to about 50% by weight, for example from about 0.1 to about 30% by weight, from about 0.5 to about from 20% by weight, from about 1 to about 10% by weight, from about 5 to about 15% by weight, or from about 2 to about 5% by weight based on the total weight of the catalyst.
    The total amount of the soot oxidation catalyst component in the soot oxidation zone will depend on the particular application, but may comprise about 0.1 to about 15 g / ino, about 1 to about 7 g / ino, about 1 to about 5 g / in, about 2 to about 4 g / in ', or about 3 to about 5 g / in of the soot oxidation catalyst component.
    In some embodiments, the soot oxidation catalyst component is supported on an inert oxide support selected from the group consisting of alumina, titania, non-zeolitic silica-alumina, ceria, zirconia and mixtures, composite oxides and mixed oxides - of either of the two or more of these.
    The soot oxidation catalyst composition can be applied to the filter substrate as an aqueous solution or as a coating layer slurry. The preferred overlay layer charge for the soot oxidation catalyst is from about 0.1 to about 05g.
    Catalysts for use in the method according to the invention are obtainable by methods known to those skilled in the art, including impregnating the support materials with aqueous transition metal salts, incipient moisture or coprecipitation. For example, the fuliszem oxidation catalyst component can be obtained by coprecipitating tungsten, cerium and zirconium.
    In other embodiments, the catalyst is obtained by coprecipitating cerium and zirconium salts, and then impregnating the resulting product with only a tungsten salt and - calcining at temperatures between <600ºC.
    Whichever preparation route is selected, it is desirable to activate the catalyst by heating in an existing environment, for example, in air, to elevated temperatures for an appropriate period, for example, at> 600ºC such as at 650ºC and above or at 700ºC and above.
    This heat activation step is particularly desirable - for a catalyst that consists of iron and tungsten dispersed in zirconia.
    The SCR catalyst for use in the diesel particulate filter is not particularly limited.
    Suitable SCR catalyst compositions include a catalyst support material and a metal.
    Examples of suitable catalyst support materials include alumina, aluminum silicates such as zeolites, silicoaluminum phosphate, aluminum phosphates, or other molecular sieves, or a mixed phase molecular sieve such as AEI / CHA, AEI / SAV, AEN / UEI, AFS / BPH, BEC / ISV, ITE / RTH, KFI / SAV, IMTT / TON, SBS / SBT, and SSF / STF, titania, ceria, zirconia, vanadate, lantana, or mixed oxide based materials.
    Particularly preferred support materials include aluminosilicate and aluminophosphate molecular sieves having a CHA, LEV, ERI, AEI, UFI, or DDR structure.
    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 some embodiments, preferred metals include vanadium (V), tungsten (W), iron (Fe), and copper (Cu), and mixtures thereof.
    In some embodiments, preferred SCR catalysts include small copper-charged molecular sieves such as baskets having an extrastructure (e.g.
    loaded with fon) 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 some embodiments, Cu: CHA SCR catalysts are particularly preferred.
    A particularly preferred SCR catalyst for the present invention is W-CeO; 7-ZrO; or Fe-WCeO7-ZrO ;. Applicants have found that the modification of such catalysts will allow it to carry out the NH; SCR while decreasing the ignition temperature of the C-O reaction. In particular, it has been found that CexZr1.xO2, where x is about 0.1 to about 0.99 is active to promote the CO reaction, and by doping these materials with W, its activities for the SCR reaction are increased. Therefore, in some embodiments, the invention belongs to the W-CeO, 7-7Z7rO, and / or Fe-W-CeO, 7-ZrO, catalyst systems; with the ability to perform both the NO reduction reaction, with NH; and soot oxidation with O ;. The loads of W, Fe, and Zr in these materials can be optimized to achieve this dual functionality.
    Some SCR catalyst compositions are typically applied to the filter as a coating layer 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 may comprise about 0.1 to about 15 g / ino, about 1 to about 7 g / ino, about | at about 5 g / in2, about 2 to about 4 g / in ', or about 3 to about 5 g / in do - SCR catalyst. The preferred coating layer charge for the SCR catalyst is about 0.1 to about 0.5 g / in.
    In a preferred embodiment, the soot oxidation catalyst and SCR catalyst are present in a ratio of about 1:25 to about 1: 2, for example, about 1:10 to about 1: 5 . In some embodiments having such soot oxidation catalyst to SCR catalyst ratios, 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 W-CeO, -ZrO, and / or Fe-W-CeO; 7-ZrO ,, where the inlet side of the filter is coated with less composition catalytic compared to the outlet side of the filter. In some other embodiments, the soot oxidation catalyst and the SCR catalyst have similar formulations except that the relative ratios of W: Fe and / or CeO ',: 7rO, are different.
    The soot catalyst and 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 effectiveness of the catalytic material, for example, increasing its operating temperature range, increasing the catalyst contact surface area, etc. Therefore, a catalyst zone comprising a catalytic component can also include additional non-catalytic components. Examples of such optional non-catalytic components may include non-doped alumina, titania, non-zeolitic 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 as long as 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, size of medium pore, etc., which are compatible with soot oxidation and SCR zones. Suitable DPF may include fibrous non-woven filters and metallic or cordierite honeycombs, as well as other types of diesel particulate filters. The preferred filter substrates for use in the mobile application are monoliths having a geometry then called honeycomb which comprises a plurality of parallel adjacent channels, each channel typically having a square, round, hexagonal, or triangular cross section. The honeycomb shape provides a large catalytic surface with minimal overall size and pressure drop. Other substrates include sheets or canvases that can be zoned in any suitable form including, for example, stacking, curling, or arrangement around a central axis. Other substrates include packaged beds that can be formed with absorbent pellets, preferably held together with a binder or precipitated to form an adherent mass. Soot filters for use in the present invention can be manufactured using a variety of materials including sintered metal, ceramic or metallic fibers, etc. A preferred type of filter is a so-called "wall flow" filter made of porous ceramic or other material in the form of a monolithic arrangement of many small channels substantially parallel over most of the length of the filter body, and in which the channels are capped at alternating ends in a manner similar to a checkerboard. Construction-specific materials for wall flow monoliths include cordierite, a-alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, silica-magnesia alumina or zirconium silicate, ceramic composite fibers, or a porous refractory metal. Preferred materials include cordierite, silicon carbide, and alumina titanate.
    Capping or capping the alternating endings of the wall flow filter channels forces the exhaust gas through the porous walls of the ceramic channel. Although porous, these walls prevent most of the particulate from passing through. That is, the exhaust gas not treated by the catalytic filter flows into the substrate channels (i.e., the filter inlet) where it communicates the upstream side of the substrate wall. During the operation of a motor, a differential pressure exists between the inlet sides and the outlet of the substrate (greater pressure on the inlet side with respect to the outlet side), and thus, a differential pressure also exits between the upstream side and downstream side of the substrate wall. This differential pressure, together with the gas-permeable nature of the walls, allows the exhaust gas flowing in a channel that is open on the inlet side, to pass from the upstream side of a porous wall to the upstream side of that wall, and then on an adjacent channel (ie, filter outlet) that is open to the downstream section of the exhaust system. The 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 flow-through wall contains about 100 to 400 cells per square inch ("cpsi").
    The current 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. However, in some embodiments, the average pore dimensions on the filter channel walls of the ceramic wall flow filter through which the exhaust gas passes varies from about 5 to about 50 µm, for example about 15 to about 30 æm. In other embodiments, the average pore size of the filter is about 10 to about 200 nm.
    In some embodiments, the 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% (for example, 45% to 75%) having an average pore size of hair - less than 5 microns (for example, 5 to 30 microns) and preferably at least 55% (for example, from 55% to 75%).
    Wall flow filters for use with the present invention preferably have an efficiency of at least 70%, at least about 75%, at least about 80%, or at least about 90
    %. In some embodiments, the effectiveness will be about 75 to about 99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about 95%. Here, the effectiveness is relative to soot and other particles of similar size and to the particulate concentrations typically found in diesel exhaust gases. For example, particulates in the diesel exhaust can vary in size from 0.05 microns to 2.5 microns. Thus, the effectiveness 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. The preferred porosity for cordierite filters is about 60 to about 75%.
    During normal operation of the exhaust system, soot and other particulates accumulate on the upstream sides of the walls which lead to an increase in back pressure. To alleviate this increase in back pressure, the filter substrates are regenerated periodically or continuously by burning accumulated soot. The combustion process is promoted by the oxidation catalyst in the soot zone. The exhaust gas that passes through the porous substrate walls also comes into contact with the SCR catalyst incorporated in the walls, thereby eliminating a larger portion of the NO components in the exhaust gas.
    The soot oxidation zone and the 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 immersed in a 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 applying pressure or vacuum, can be used to promote adequate, uniform, and / or faster 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 filter outlet channels are immersed in 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 applying pressure or vacuum, can be used to promote adequate, uniform, and / or faster permeation of a particular coating. The SCR zone is then dried. One or more of the dipping processes can be repeated to obtain the desired coating level. After suitable catalyst loads are obtained, the catalytic coating is activated, preferably at a temperature of about 100 ° C to about 300 ° C for about 1 to about 3 hours. The activated filter is calcined to remove additional moisture at a temperature of about 450ºC to about 550ºC for about 1 to about 3 hours. A preferred method of application is AID. The drying and calcination steps are preferably carried out as for standard CSF preparation conditions.
    Another aspect of the invention is directed to a system for treating the flaring 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 others, but interact with each other to form a coherent scheme for treating the gas exhaust. Preferably, one or more of the exhaust gas component systems 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 reducer into the exhaust gas, wherein the injector or other device is arranged upstream of the filter. The inventors found that the soot oxidation zone of the filter will not consume a nitrogen-based reducer (urea, ammonia, etc.) that is necessary for the SCR reaction downstream. Therefore, the present invention allows a reducer to be dosed in the exhaust gas upstream of the filter containing the soot oxidation catalyst. In some embodiments, the system also comprises an exhaust gas stream generated by a low-combustion internal combustion engine, one or more ducts to carry out the exhaust gas flow, in which the ducts are in fluid connection with hair. minus some of the components of the exhaust system, and / or a source of nitrogen reducer. The injector can continuously, periodically, or intermittently introduce the reducer, such gaseous ammonia, ammonia in aqueous solution, aqueous urea, or ammonia from an ammonia generator, into the exhaust gas in an effective dose to optimize the reaction of SCR downstream. The injector is in fluid communication with the exhaust gas stream and can be connected to, connected to, and / or integrated with a conduit, such as a pipe, to direct the exhaust through at least a portion of the exhaust gas system. exhaust. The injector can also be in fluid communication with a reducing agent supply tank to provide repeated injections of the reducing agent.
    In a particular embodiment, the measurement is - controlled in response to the amount of nitrogen oxides in the determined exhaust gas either directly (using a suitable No sensor) or indirectly, such as using pre-correlated tables or stored on maps in the control means that correlate one or more of the aforementioned inputs indicative of an engine condition with the NO content, - of the predicted exhaust gas. The measurement of the nitrogen reducer can be arranged such that 60% to 200% of the theoretical ammonia is present in the exhaust gas that enters the SCR catalyst calculated in 1: 1 NH3 / NO and 4: 3 NH3 / NO ;. The control means can comprise a pre-programmed processor such as an electronic control unit (ECU). Measurement control involves limiting the introduction of the nitrogen reducer into the flowing exhaust gas only when it is determined that the SCR catalyst is able to catalyze the NO reduction, at or above a desired efficacy, such as above 100ºC, above 150ºC or above 175ºC. The determination —the control method can be aided by one or more suitable sensor inputs indicating an engine condition selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, gas mass flow exhaust system, pipe distribution system vacuum, ignition time, engine speed, exhaust gas lambda value, the amount of fuel injected into the engine, the position of the exhaust gas recirculation valve (EGR) and thus, the amount of EGR and impulse pressure. In some preferred embodiments, the injector is arranged upstream of the dual-function catalytic filter with no interposed SCR or other catalytic components between the injector and the filter. That is, the NH; in the exhaust stream it is not consumed or otherwise used after it enters the exhaust gas stream and before communicating the SCR zone of the filter.
    In another embodiment, all or at least a portion - of the nitrogen-based reducer, particularly NH; 3, can be provided by a NO absorbent catalyst (NAC), a NO trap, poor (LNT), or a NOx storage / reduction catalyst (NSRC), arranged upstream of the dual-function catalytic filter. One of the functions of NAC in the present invention is to provide a source of NH; for the SCR downstream reaction. - Therefore, the NAC is configured in the system in a manner similar to that of the injector - that is, upstream of the dual-function catalytic filter and preferably without any interposed SCR or other catalytic components between the NAC and the filter. The NAC components useful in the present invention include a catalyst combination of a base material (such as alkali metal, alkaline earth metal or a rare earth metal, including alkali metal oxides, alkaline earth metal oxides, and combinations thereof), and a precious metal (such as platinum), and optionally a reducing catalyst component, such as rhodium.
    Specific types of basic material useful in 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, such as 20 to 60 g / ft. Alternatively, the precious metal of the catalyst is characterized by the average concentration which can be from about 40 to about 100 grams / ft. Under certain conditions, during periodically rich regeneration events, NH; can be generated on a NO absorbent catalyst. The SCR catalyst downstream of the NO adsorbent can improve the NO reduction efficiency of the general system.
    In the combined system, the SCR catalyst is capable of storing NH; released from the NAC catalyst during rich regeneration events and uses the NH; 3 stored to selectively reduce some or all of the NO, which escapes through the NAC catalyst during normal poor operating conditions.
    In some embodiments, the system also - comprises a diesel oxidation catalyst (DOC) to oxidize the soluble organic fraction (SOF) based on hydrocarbons and the carbon monoxide content of the diesel exhaust through simple oxidation: CO + 14 O; 3 CO; [HC] + O; 3 CO; + HO DOC can also serve to oxidize NO to NO ;, which in turn can be used to oxidize particulate matter in the particulate filter. - In addition, DOC can be used to reduce particulate matter (PM) in the exhaust gas.
    Preferably, the DOC is arranged upstream of the dual-function catalytic filter, and more preferably upstream of the reducing SCR injector or NAC.
    In another embodiment, an oxidation catalyst for oxidizing nitrogen monoxide in the exhaust gas to nitrogen dioxide can be located upstream of a measurement point of the nitrogen reducer in the exhaust gas.
    In one embodiment, the oxidation catalyst is adapted to produce a gas stream that enters the zeolitic SCR catalyst having a NO to NO ratio, from about 4: 1 to about 1: 3 by volume, for example, at an exhaust gas temperature at the oxidation catalyst inlet from 250ºC to 450ºC: In another embodiment, the system also comprises a Closed Pair Catalyst (CCC) upstream of the DOC.
    The oxidation catalyst may include at least one platinum group metal (or some combination thereof), such as platinum, palladium, or rhodium, coated on a direct flow monolith substrate.
    Other metallic catalysts that can be used in DOC include aluminum, barium, cerium, alkali metals, alkaline earth metals, rare earth metals, or any combination of these.
    In one embodiment, the at least one metal in the platinum group is platinum, palladium or a combination of both - platinum and palladium.
    The platinum metal group can be supported on a high surface area coating layer component such as alumina, a zeolite such as a zeolite aluminosilicate, silica, non-zeolitic silica-alumina, ceria, zirconia, titania or a mixed oxide or composite containing both ceria and zirconia.
    In a preferred embodiment, the diesel oxidation catalyst composition contains about 10 to 120 g / ft of a platinum group metal (for example, platinum, palladium or rhodium) dispersed on a high surface area refractory oxide support (for example, y-alumina). In some embodiments, one or more additional SCR catalyst components may be included in the system, preferably downstream of the dual-function catalytic filter, to again reduce the NO concentration in the exhaust gas. For example, at the outlet of the dual-function catalytic filter, the exhaust gas passes through a direct flow substrate coated with an SCR catalyst. In this way, the direct flow SCR catalyst is arranged downstream of the dual-function catalytic filter. The concentration of NO in the exhaust gas is reduced as the gas passes through the dual-function catalytic filter and then is reduced again as the gas passes sequentially through one or more - direct flow SCR substrates. In another embodiment, the system also comprises an additional reducing injector upstream of the direct flow SCR catalyst and downstream of the dual-function catalytic filter. In some embodiments, the one or more direct flow SCR catalysts downstream are articles subjected to extrusion.
    The number of additional direct-flow SCR catalyst components can be any practical number, such as 1, 2, 3, or 4. The SCR catalyst (s) downstream may be the same or different from the catalyst for SCR coated on the dual-function catalytic filter. In some embodiments, preferred SCR catalysts include small pore molecular sieves loaded with copper such as chabazites having an additional structure or free copper, including Cu: SSZ-13 and Cu: SAPO-34. In some embodiments, the system also comprises an ammonia release catalyst disposed downstream of the dual-function catalytic filter, and in some embodiments, downstream of the direct flow SCR components. The ASC serves to oxidize most, if not all, of the ammonia before emitting the exhaust gas into the atmosphere or passing the exhaust gas through a recirculation loop before the exhaust gas enters / re-enters the engine. In this way, ASC reduces the concentration of ammonia released from the SCR reaction, the release of ammonia from the catalyst surface during rapid temperature rise, or the use of a stoichiometric excess of reducer. Preferably, the ASC material should be selected to favor ammonia oxidation rather than NO, or N, O formation. Preferred catalyst materials include platinum, palladium, or a combination thereof, with platinum or a platinum / palladium combination being preferred. Preferably, the catalyst is arranged on a high surface area support, including, but not limited to, alumina. In some embodiments, ASC is applied to a substrate, preferably substrates that are designed to provide great surface contact with minimal back pressure, such as direct flow metallic honeycombs or cordierite. For example, a preferred substrate has between about 25 and about 300 cells per square inch (CPST) to ensure low back pressure. Obtaining a low back pressure is particularly important to minimize the effect of ASC on the performance of low pressure EGR. ASC can be applied to the substrate as a coating layer, preferably to obtain a charge of about 0.3 to 2.3 g / in ”. To provide another NO conversion, the front of the substrate can be coated only with the SCR coating, and the rear coated with SCR and an NH oxidation catalyst; such as Pt or Pt / Pd with an alumina support.
    Another aspect of the invention relates to a method by which nitrogen oxides are reduced with a nitrogen reducing agent, preferably at a temperature of at least 100 ° C, such as from about 150 ° C to 750 ° C. In some embodiments, the —method comprises the steps of flowing a soot-poor exhaust gas containing NO, and a nitrogen reducing agent, preferably NH; through a dual-function catalytic filter of the present invention in that the exhaust gas coming out of the filter has a reduced concentration of soot and NO, compared to the exhaust gas flowing through the filter. The method may also comprise one or more of the following steps: (a) accumulating and / or burning the soot that is in contact with the dual-function catalytic filter inlet; (b) introducing a nitrogen reducing agent into the exhaust gas stream before communicating the dual-function catalytic filter, preferably without interposed catalytic steps involving the NO treatment, and the reducer; (c) generating NH; on a NO absorbent catalyst, and preferably using such an NH; as a reducer in a downstream SCR ration; (d) communicate the exhaust gas stream with a DOC to oxidize the soluble organic fraction based on hydrocarbon (SOF) and / or carbon monoxide in CO ;, and / or oxidize NO to NO ;, which in turn , can be used to oxidize particulate matter in the particulate filter; and / or reduce the particulate matter (PM) in the exhaust gas; (e) communicating the exhaust gas with one or more direct flow SCR catalyst devices in the presence of a reducing agent to also reduce the NOx concentration in the exhaust gas, wherein the one or more flow SCR catalyst devices direct are preferably disposed downstream of the dual-function catalytic filter; and (f) communicating the exhaust gas with an ammonia release catalyst, preferably downstream of the dual-function catalytic filter and, if present, the one or more direct flow SCR catalyst devices to oxidize most, if not all , ammonia before emitting exhaust gas into the atmosphere or passing exhaust gas through a recirculation cycle before exhaust gas enters / re-enters the engine.
    In a particular embodiment, the temperature range for the SCR reaction is 175 to 550ºC.
    In another embodiment, the temperature range is 175 to 400ºC: In another embodiment, the temperature range is 450 to 900ºC, preferably 500 to 750ºC, 500 to 650ºC, 450 to 550ºC, or 650 to 850ºC .
    In a particular embodiment, the reduction of nitrogen oxides is carried out in the presence of oxygen.
    In the method according to the invention, the addition of nitrogen reducer can be controlled so that the NH; at the entry of the catalyst it is controlled to be 60% to 200% of the theoretical ammonia calculated at 1: 1 of NH; / NO and 4: 3 of NH; 3 / NO ;. In some embodiments, the ratio of nitrogen monoxide to nitrogen dioxide in the inlet gas of the catalyst is 4: 1al: 3volume. In this regard, the ratio of nitrogen monoxide to nitrogen dioxide in the gas can be adjusted to oxidize nitrogen monoxide to nitrogen dioxide using an oxidation catalyst located upstream of the catalyst. The nitrogen reducing agent can be derived from any suitable source including ammonia itself, hydrazine or an ammonia precursor selected from the group consisting of urea ((NH>); CO), ammonium carbonate, ammonium carbamate, hydrogen carbonate ammonium and ammonia shape. NH; it can also be supplied by a poor NOx pickup or similar device arranged upstream of the dual function filter. The method can be carried out on a gas derived from a combustion process, such as an internal combustion engine (mobile or stationary), a gas turbine and coal or oil power plants. The method can also be used to treat gas from industrial processes such as refining, from heaters and furnaces to refineries, furnaces, chemical processing industry, coke ovens, municipal waste plants and incinerators. In a particular embodiment, the method is used to treat exhaust gases from a low-burning vehicle internal combustion engine, such as a diesel engine, a low-burning gasoline engine or an engine powered by liquefied petroleum gas or natural gas.
    EXAMPLES The following non-limiting examples are provided to demonstrate the particular aspect of some embodiments of the invention. Example 1: Physical mixtures of simulated diesel exhaust soot from cordierite compositions, CeO7-ZrO ,, WCeO, 7-ZrO; (5% by weight of W), W-CeO; 7-7rO; (15% by weight of W), were prepared as powders. These powders were tested in a TPO-type experiment whereby the mixture is elevated in a mixture of gases containing He and 5% O ;. The soot ignition temperature is measured by the formation of CO ;. The results of these tests are provided in Figure 4. In particular, CexZr- xO2 (x = 1.0) promotes soot oxidation and the ignition temperature is decreased from a temperature of around 600ºC in the absence of a catalyst to a temperature of about 450ºC 'The presence of W slightly decreases the reactivity.
    Example 2: The compositions of CeO7-7ZrO ,, W-CeO, 7-7rO, (5% by weight of W), W-CeO7-7rO, (15% by weight of W), were prepared as powders. These powders were tested in a micro-reactor to determine the effect of tungsten on NO reduction activity, CeO; -7rO ;. The results of these tests are provided in Figure 5. As the results show, the presence of W increases the NO reduction activity, of CeO; 7-ZrO ;.
    Example 3: The compositions of W-CeO,; 7rO ;, and W-CeO ;, were - prepared as powders. These powders were tested in a micro-reactor to determine the effect of ZrO, in the NO-reducing activity. The results of these tests are provided in Figure 6. As the results show, a W-CeO catalyst is effective for reducing NO.
    Example 4: The CeO, 7rO, and W-CeO; -7rO compositions were coated in SiC direct flow filter cores (1 inch (2.54 in) in diameter and 7 inches (17.78 cm) in length ) at a load of about 0.3 g per cubic inch. The soot oxidation activities of these coated filters were first measured by loading them with the soot produced during the combustion of Diesel Fuel US 06. The filter was loaded at about 10 to 20 mg of soot per cubic inch. The soot oxidation experiment was carried out in a gas mixture of N, with 10% O; in a -60K hr 'GHSV monitoring the back pressure. The exposed filter without containing any catalyst without any soot shows an increase in back pressure with increasing temperature due to changes in the kinetic energy of the gas. The exposed filter loaded with soot showed a greater initial back pressure compared to the clean filter and then a drop in pressure at a temperature of around 550ºC caused by the oxidation of soot. This drop in back pressure occurs at a temperature less in the filter coated with the CeO7-7rO catalyst; and W-CeO7-7rO; due to its promotion of combustion in the soot process. The results of this example are shown in Figure 7.
    Example 5: The cores prepared in Example 4 were measured for their NH SCR activities. The coated filter catalyst was measured in a gas mixture containing 500 ppm NO, 500 ppm NH; 3.5% CO ;, 5% H, O, 10% O; and 300 ppm CO. Although CeO7-ZrO ,; it was inactive and not selective to react NOX with NH ;, the WCeO catalyst, - —ZrO; shows high reactivity for the NH3-SCR reaction. The results of this example are shown in Figure 8.
    权利要求:
    Claims (20)
    [1]
    1. Article to treat an exhaust gas, characterized by the fact that it comprises: a) a soot filter having an inlet and an outlet, b) a zone at the soot oxidation inlet, where the soot oxidation zone comprises a component soot oxidation catalyst consisting essentially of at least one transition metal dispersed in a mixed cerium and zirconia oxide and / or composite, 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 c) an SCR zone at the outlet, wherein the SCR zone comprises a catalytic SCR component.
    [2]
    2. Article according to claim 1, characterized by the fact that the catalytic component is supported on an inert oxide selected from the group consisting of alumina, titania, non-zeolitic silica-alumina, ceria, zirconia and mixtures, composite oxide and mixed oxides of any two or more of these.
    [3]
    3. Article according to claim 1, characterized by the fact that said soot oxidation catalytic component has a formula of M: Ce, O, Zr1..02, where x = 0.1 to 0.9 and M is selected from W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations of these.
    [4]
    4. Article according to claim 3, characterized by the fact that M is W and x is less than about 0.5.
    [5]
    5. Article according to claim 1, characterized by the fact that at least one transition metal is present in the soot oxidation catalyst component from 0.5 to 20% by weight, based on the total weight of the catalyst component soot oxidation.
    [6]
    6. Article according to claim 1, characterized in that said soot oxidation zone is coated with a soot oxidation catalyst comprising said soot oxidation component and, optionally, one or more binders or stabilizers non-catalytic.
    [7]
    7. Article according to claim 1, characterized in that said soot oxidation zone comprises said soot oxidation component in an amount of about 0.1 to about 0.5 g / in.
    [8]
    8. Article according to claim 1, characterized by the fact that said SCR catalyst component comprises at least one metal selected from V, Cr, Ce, Mn, Fe, Co, Ni or Cu, in which the metal is arranged on a support selected from aluminosilicate molecular sieves, silicoaluminophosphate molecular sieves, alumina, and mixed oxide base material.
    [9]
    9. Article according to claim 1, characterized in that said SCR catalyst component is a molecular sieve having a CHA structure and an extrastructure copper.
    [10]
    10. Article according to claim 1, characterized by the fact that said soot oxidation catalyst component has a formula W: CexO3Zr1-xO2, where x = about 0.1 to about 0.9 and said catalyst component of SCR has a formula FeW: Ce, x03Zr1.O> 2, where x ”= about 0.1 to about 0.99.
    [11]
    An article according to claim 10, wherein x is less than about 0.5 and x * is greater than about 0.5.
    [12]
    12. An article according to claim 10 characterized by the fact that said SCR catalyst component has a W: Fe ratio of more than about 0.5.
    [13]
    13. Article according to claim 1, characterized in that said soot oxidation catalyst component and said SCR catalyst component have the formulation and in which said soot oxidation catalyst component at the entrance and said component SCR catalyst at the outlet are present in a ratio of about 1:25 to about 1: 2.
    [14]
    14. Article according to claim 1, characterized by the fact that said SCR catalyst is a small pore aluminosilicate or molecular sieve of silicoaluminophosphate having extrastructure copper.
    [15]
    15. Article according to claim 1, characterized by the fact that said soot filter is a wall flow filter.
    [16]
    16. System for treating NOx in a low-burning exhaust gas, characterized by the fact that it comprises: a) a nitrogen-reducing agent injector, b) a dual-function catalytic filter comprising
    1. a soot filter having an inlet and an outlet,
    1. a soot oxidation center zone, where the soot oxidation zone comprises a catalytic soot oxidation component which consists essentially of at least one transition metal dispersed in a mixed cerium and zirconia oxide and / or composite , in which at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, and ii. an SCR zone at the outlet, wherein the SCR zone comprises a catalytic SCR component, wherein said injector is arranged upstream of, and is in - fluid communication with, said dual function catalytic filter.
    [17]
    17. System according to claim 16, characterized in that said system is free of a filter substrate that is not coated with a soot oxidation catalyst and an SCR catalyst.
    [18]
    18. The system according to claim 16, characterized by the fact that it also comprises: c) at least a direct flow monolith substrate coated with a second SCR catalyst composition disposed downstream of the dual-function catalytic filter; and d) an ammonia release catalyst disposed downstream of said at least one direct flow monolith substrate coated with said second SCR catalyst composition.
    [19]
    19. System according to claim 16, characterized by the fact that it also comprises: e) a diesel oxidation catalyst disposed upstream of said nitrogen reducing agent injector.
    [20]
    20. Method for treating a low-burning exhaust gas, characterized by the fact that it comprises: a) a stream of low-burning exhaust gas comprising soot, NOx, and a nitrogen reducing agent through a catalytic filter of dual function that comprises i a filtertreatigem enting an input and an output, ii. a soot oxidation inlet zone, where the soot oxidation zone comprises a soot oxidation catalytic component consisting essentially of at least one transition metal dispersed in a mixed cerium and zirconia oxide and / or composite, in that at least one transition metal is selected from the group consisting of W, Cr, Ce, Mn, Fe, Co, Ni, Cu, and combinations thereof, and ill. an SCR zone at the outlet, wherein the SCR zone comprises a catalytic SCR component, b) oxidizing at least a portion of the soot in the soot oxidizing zone; and c) reducing at least a portion of said NOx in the SCR catalyst zone.
    Figure 1. =
    SAS SS Catalyst zone of - É MNE [Catalyst zone of SCR CM O 12 15 Figure 2 29 21 O to 26 Ú 27 22:. 24 '
    Figure 3 Injector A and Mixer n Figure 4
    7.0E-09 E 15W-Ce02-2r02 A 60:09 À] «m5W-Ce02-2r02 FA GS 5000 o - o | -—— Cordierita SA o 4.0E-09 7 NS O. SAR & £ 30000 st $ 4 re: = * ME AS
    2.0E-09 E & à
    1.08-09 FE E MN OS 00:00 SSSSSSSSSSSSSSSS anna casas O SERSSSE 150 250 350. 450 550 650 Temperature (ºC): 1
    Figure 5 100 OETEET reoisEgooEESS, so a s - É A »Ed dA cc A = 7 dE dd Jews] À | And E. q rt “e-CeO02-7r02 as to À III,: Fso. o 2 »will the SS 150 200 250 300 350 400 450 500 550 600 Temperature (* C) Figure 6 = the F * x and THESE ã & di)> Y Oo n; - = É ow 4 Fo dA u É ao fo
    SHE 2 30 FAITH 8 nl DZ “E-W-Ce02 | : the 150 200 250 300 350 400 450 500 550 Temperature (ºC) is
    Figure 7. Po so -> Ro intend Pa e to a saves & a ododrtrtr tr iaes << E ecc adN Be Fo aee ». “E DPF rig wo exposed“ DPF w w exposed: ES “* soot DPF w coated with CaO02-2rO:“ soot DPF w coated with W-Ce02-2602 o, 100 200 300 400 500 600 Temperature (ºC) Figure 8 100 m— 99 |] = ceo22r02. this W-Ce02-2r02 are 70 qo ga cr i 60 50 4th od i 20: .— & Ao CAT SAE CS 1. o ”150 200 250 300 350 400 450 500 550. Temperature (ºC)
    Figure 9 100 SS 80 amas PASTEES POMENTA o o. à 70 = io ERA> RL fa 'i et Zzs + - o Po SS o ss EE A mm v S 4o Í. = ind dd 200 BM
    SPA O la * o 150 200 250 300 350 400 450 500 550. Temperature (ºC)
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    法律状态:
    2020-08-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-08-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 8A ANUIDADE. |
    2020-12-01| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US201161491870P| true| 2011-05-31|2011-05-31|
    US61/491870|2011-05-31|
    PCT/US2012/040064|WO2012166833A1|2011-05-31|2012-05-31|Dual function catalytic filter|
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