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    • 专利摘要:
    emission treatment system downstream of a direct gasoline injection engine, catalyzed particulate filter, and methods of treating an exhaust gas and making a catalyzed particulate filter are provided exhaust systems and components suitable for use together with gasoline engines to capture particulates, in addition to reducing gas emissions, such as hydrocarbons, nitrogen oxides and carbon monoxide. exhaust treatment systems that comprise a three-way conversion catalyst (twc) located in a particulate filter are provided. coated particulate filters having washable coating loads in the range of 1 to 4 g / ft (g / 0.305 m) result in minimal impact on back pressure while simultaneously providing twc catalytic activity and particle trapping functionality to meet ever-changing regulations stricter ones, such as the euro 6. high enough levels of oxygen storage components (osc) are also displayed on and / or inside the filter. the filters may have a coated porosity that is substantially the same as their uncoated porosity. the catalytic material twc may comprise a particle size distribution such that a first set of particles has a first particle size d90 of 7.5 (mi) m or less, and a second set of particles has a second particle size d90 of more than 7.5 (mi) m. methods of making and using them are also provided.
    公开号:BR112012026943B1
    申请号:R112012026943-7
    申请日:2011-04-19
    公开日:2020-12-15
    发明作者:Mirko Arnold；Stephan Siemund；Attilio Siani；Knut Wassermann
    申请人:Basf Corporation；Basf Se；
    IPC主号:
    专利说明:

    REMISSIVE REFERENCE TO RELATED ORDERS
    [1] This application claims priority under 35 USC §119 (e) of US patent applications 61 / 325,478, filed on April 19, 2010 and 61 / 386,997, filed on September 27, 2011, each of which is incorporated here as a reference in its entirety. TECHNICAL FIELD
    [2] The present invention relates generally to emission treatment systems with catalysts used to treat gas flows from gasoline engines containing hydrocarbons, carbon monoxide, and nitrogen oxides in combination with particulate material. More specifically, the present invention is directed to three-way conversion catalysts (TWC) or oxidation catalysts, coated on and in particulate material filters, such as soot filters. BACKGROUND
    [3] Particulate matter emissions for gasoline engines are being subject to regulations, including future Euro 6 standards (2014). In particular, certain gasoline direct injection (GDI) engines have been developed whose operating regimes result in the formation of fine particulate material. Existing after-treatment systems for gasoline engines are not suitable for obtaining the proposed particulate material standard. In contrast to particulate materials generated by diesel combustion engines, particulate materials generated by gasoline engines, such as GDI engines, tend to be thinner and in smaller quantities. This is due to the different combustion conditions of a diesel engine compared to a gasoline engine. For example, gasoline engines run at a higher temperature than diesel engines. In addition, hydrocarbon components differ in emissions from gasoline engines compared to diesel engines.
    [4] Emission standards for unburned hydrocarbons, carbon monoxide and nitrogen oxide contaminants continue to become more stringent. To meet these standards, catalytic converters containing a three-way conversion catalyst (TWC) are located in the exhaust gas line of internal combustion engines. Such catalysts promote oxidation by oxygen in the gas stream of unburned hydrocarbons and carbon monoxide, as well as the reduction of nitrogen oxides to nitrogen.
    [5] A catalyzed particulate material collector comprising a TWC catalyst coated on or in a particulate material collector is provided in US patent application publication 2009/0193796 (Wei). The TWC catalyst can be coated on an inlet side, an outlet side or both of the filter.
    [6] Volume limiting and back pressure discharge systems can limit the ability to add additional treatment components. In some GDI emission systems, two or more TWC catalyst composites in combination with NOx collectors and SCR catalysts are required to achieve emission standards. It is a challenge for such systems to accommodate any additional tiles or cartridges along the discharge pipe.
    [7] As particulate material standards become more stringent, however, there is a need to provide particulate material retention functionality without unduly filling the discharge pipe and increasing back pressure. In addition, HC, NOx and CO conversions continue to be of interest. Certain filter technology has relatively small pores and / or less porosity designed to capture fine particulate matter, however, such filters cannot generally accommodate sufficient catalyst load to meet the requirements for HC, NOx and CO conversion.
    [8] There is an ongoing need to provide a catalyzed filter that provides sufficient TWC in combination with an efficient filter without unduly increasing back pressure so that regulated HC, NOx and CO conversions can be achieved while meeting particulate matter emissions. SUMMARY
    [9] Discharge systems and components suitable for use in combination with gasoline engines are provided to capture particulate materials in addition to treating gaseous emissions such as hydrocarbons, nitrogen oxides and carbon monoxides. it is of interest to provide a particulate material filter for gasoline engines (GPFs or PFGs) that provides full three-way conversion (TWC) functionality with minimal impact on back pressure. It is recognized that a TWC catalyzed filter may need to be used in combination with a second TWC catalyst to meet car manufacturer regulations and requirements. Particulate matter from gasoline engines is generated mainly during cold start. This is in contrast to the way in which particulate material is generated from diesel engines, which is for the entire operation of the engine at an approximately constant rate.
    [10] Aspects include discharge treatment systems comprising a three-way conversion catalyst (TWC) coated over and / or a particulate filter in a direct gasoline engine emission treatment system for treating a discharge flow comprising hydrocarbons, carbon monoxide, nitrogen oxides and particulate material.
    [11] A first aspect provides a catalyzed particulate material filter whose coated porosity is substantially equal to its uncoated porosity. That is, such a coated filter results in a back pressure or pressure drop that is not detrimental to the performance of the engine. A non-harmful pressure drop means that the engine will generally perform the same (for example, fuel consumption) in a wide range of engine operating modes in the presence of a filter substrate that is in a coated or uncoated state. One or more detailed modalities provide that uncoated porosity and coated porosity are comprised of 7% (or 6%, or 5%, or 4%, or 3%, or 2.5%, or 2% or even 1% ) each other. The porosity of the filter, coated or uncoated, is measured in the filter. One way to measure porosity is to section the filter, measure the porosity of each section, and mediate the results. For example, a filter can be divided into an input / front part and an output / rear part, the porosity of each part can be taken, and the results can be measured.
    [12] Another aspect provides a catalyzed particulate material filter comprising a three-way conversion catalytic material (TWC) that is present in or on the filter in an amount of at least 1.0 g / in.3 (61 g / L). A detailed modality provides that the amount is 1.0 to 4.0 g / inch.3 (61 g / L to 244 g / L), or 1.5 to 4.0 g / inch.3, or even 2, 0 to 4.0 g / inch.3. Another detailed aspect provides a catalyzed particulate material filter located in an emission treatment system downstream of a gasoline direct injection engine to treat a discharge flow comprising hydrocarbons, carbon monoxide, nitrogen oxides, and material in particles, the catalyzed particulate material filter comprising: a three-way catalytic conversion material (TWC) which is coated on or in a particulate material filter in an amount in the range of 1.0 to 4.0 g / in .3 (61 to 244 g / L); where the TWC catalytic material stores at least 100 mg / L of oxygen after a full aging life and comprises an oxygen storage component in an amount in the range of 1.0 to 4.0 g / in.3 (61 g / L to 244 g / L); wherein the particulate filter comprises a pore size distribution such that a first set of pores has a first average pore size of 30 μm or less and the second set of pores has a second average pore size greater than 30 μm; and wherein the TWC catalytic material comprises a particle size distribution such that a first set of particles has a first average particle size of 7.5 μm or less and a second set of particles has a second average particle size greater than 7.5 μm.
    [13] In one or more modalities, the uncoated porosity and the coated porosity are in the range of 55 to 70%. In another embodiment, the particulate material filter comprises an average pore size in the range of 15 - 25 μm. In yet another modality, the coated and uncoated porosities are in the range of 60 to 70% and the particulate material filter has an average pore size in the range of 18 - 23 μm. Certain embodiments can provide that the catalyzed particulate material filter, that is, the coated filter, can also comprise an average pore size in the range of 13 - 23 μm (or even 16 - 21 μm).
    [14] The particulate filter can comprise a pore size distribution such that a first set of pores has a first average pore size of 30 μm or less and a second set of pores has a second average pore size greater than 30 μm. The first average pore size can be in the range of 5 - 30 μm and the second average pore size can be in the range of 30 - 300 μm. The first average pore size can be in the range of 10 to 30 μm and the second average pore size can be in the range of 30 to 100 μm.
    [15] The TWC catalytic material may comprise a particle size distribution such that a first set of particles has a first d90 particle size of 7.5 μm or less and a second set of particles has a second particle size. d90 greater than 7.5 μm. The first average particle size can be in the range of 1 - 7.5 μm (or 1 - 6.5 μm, or 1 - 6.0 μm or 1 - 5.5 μm, or even 1 - 5.0 μm) and the second average particle size can be in the range of 7.6 - 100 μm (or 10 - 100 μm, or 15 - 100 μm or 20 - 100 μm or 30 - 100 μm or even 50 - 100 μm). A particle size d90 refers to the point on the particle size distribution curve that provides the point of 90% of the particles having a size equal to or less than d90. In other words, only 10% of the particles will have a particle size that is larger than d90. The TWC catalytic material can comprise the second set of particles in an amount of 10% or more by weight, such as 10-50% (or 10-40% or 10-30% or even 10-20%) by weight. A detailed embodiment provides that the first d90 particle size is 6.0 μm or less and the second d90 particle size is 10.0 μm or more.
    [16] One modality provides that the TWC catalytic material stores at least 100 mg / L (or even 200 mg / L) of oxygen after aging of the total useful life. A detailed embodiment provides that the oxygen storage component is present in an amount in the range of 1.0 to 4.0 g / in3 (61 g / L to 244 g / L).
    [17] The TWC catalytic material may comprise a wash layer comprising a platinum group metal and an oxygen storage component. One or more modalities provide for the washing layer to be provided in a single layer. The wash layer can be provided on the inlet side, the outlet side or both of the particulate filter. The wash layer may comprise rhodium, palladium, cerium or a composite of cerium, and alumina. As desired, the wash layer may be free of alumina (that is, no alumina is deliberately added to the wash layer, however, it may be present in residual amounts), simply comprising, for example, rhodium, palladium, and cerium or a cerium composite.
    [18] In one embodiment, a first layer of a single wash layer is present on the inlet side over 100% of the axial length of the particulate material filter and a second layer of a single wash layer is present on the outlet side. over 100% of the axial length of the particulate filter. In another embodiment, a first layer of single wash layer is present on the inlet side over 50 to 75% of the axial length of the particulate material filter from the upstream end and a second layer of single wash layer is present on the outlet side over 50 to 75% of the axial length of the particulate filter from the downstream end. Yet another embodiment provides that a first layer of a single wash layer is present on the inlet side over up to 50% of the axial length of the particulate filter from the upstream end and a second layer of a single wash layer is present. present on the outlet side up to 50% of the axial length of the particulate filter from the downstream end.
    [19] The particulate filter can comprise cordierite, alumina, silicon carbide, aluminum titanate or mullite.
    [20] Additional modalities include catalyzed filters having an upstream zone and a downstream zone both comprising a platinum group metal, as a palladium component, wherein the upstream zone comprises the platinum group metal in an amount that is greater than the amount of the platinum group metal in the downstream zone.
    [21] Methods of treating a discharge gas comprising hydrocarbons, carbon monoxide, nitrogen oxides and particulate materials are also provided. The methods comprise: providing a catalyzed particulate material filter comprising a three-way converting catalytic material (TWC) coated on or in a particulate material filter in an amount effective to provide an even greater number of particulate material emissions than 6 x 1011 per kilometer; locate the catalyzed particulate filter downstream of a gasoline direct injection engine; and contacting exhaust gas from the gasoline direct injection engine with the catalyzed particulate material filter.
    [22] The methods may further comprise providing full TWC functionality through the catalyzed particulate material filter, a TWC catalyst on a direct flow substrate, or combinations thereof.
    [23] Detailed modalities provide that the number of particulate matter emissions is no more than 4.0 x 1011 per kilometer, no greater than 3.0 x 1011 per kilometer, or even no greater than 2.0 x 1011 per kilometer .
    [24] Methods of making catalyzed particulate material filters are also provided. The methods include: providing a particulate material filter; provide a three-way catalytic conversion material (TWC); and coating the TWC catalytic material on or in the particulate material filter in an amount of at least 1.0 g / in3 (61 g / L) to form the catalyzed particulate material filter such that the material filter in catalyzed particles have a coated porosity that is substantially equal to an uncoated porosity of the particulate material filter.
    [25] Another aspect provides a method of treating a discharge gas comprising hydrocarbons, carbon monoxide, nitrogen oxides and particulate material, the method comprising: locating the emission treatment system of any of the modalities prior to the downstream of an engine direct gas injection and contact engine exhaust gas with the catalyzed particulate filter. BRIEF DESCRIPTION OF THE DRAWINGS
    [26] Figure 1 is a schematic view showing an engine emission treatment system according to a detailed modality.
    [27] Figure 2 is a schematic view showing an integrated engine emission treatment system according to a modality.
    [28] Figure 3 is a perspective view of a wall flow filter substrate; and Figure 4 is a sectional view of a section of a wall flow filter substrate.
    [29] Figure 5 is a graph of catalyst pressure drop as a function of engine speed for modes of various porosities. DETAILED DESCRIPTION
    [30] Discharge systems and components suitable for use in combination with gasoline engines, such as gasoline direct injection engines (GDI), are provided to capture particulate materials in addition to reducing gaseous emissions such as hydrocarbons, nitrogen oxides, and monoxides of carbon. In general terms, such gasoline engines operate as stoichiometric (X = 1), although certain GDI engines may use a poor regime (X> 1). Volume and back pressure limitations on gasoline discharge systems, however, can limit the ability to add additional treatment components. It is a challenge for such systems to accommodate any additional tiles or cartridges along the discharge pipe. As particulate material standards become more stringent, however, there is a need to provide particulate material retention functionality without unduly increasing back pressure. Applicants have found that the catalyzed particulate material filters for gasoline engines (GPFs or PFGs) can be designed with full TWC functionality while achieving proper filtration efficiency of fine gasoline engine particulate matter. In a first aspect, particulate material filters that have a pore size distribution with two or more average pore sizes, (which is an asymmetric pore size distribution) can be coated as desired with wash layers having sizes of specified particle. In this way, the pores of varying size of the filter, in combination with the surfaces of the filter wall, can be catalyzed for TWC functionality with minimal impact on back pressure while the filter efficiency is enhanced by the presence of a wash layer in the larger pores. In a second aspect, wash layer levels (for example, 1 to 4 g / in.3) are loaded onto particulate material filters with minimal impact on back pressure while simultaneously providing TWC catalytic activity and particle retention functionality for meet increasingly stringent regulations such as Euro 6. Sufficient to high levels of oxygen storage components (OSC) are also provided in and / or in the filter. Filters can have a coated porosity that is substantially equal to their uncoated porosity. That is, a coated filter has a back pressure similar to an uncoated filter in such a way that there is minimal impact on the overall engine group energy performance. In a third aspect, the time it takes the catalyst to arrive at the optimized operation of the particulate material filter can be achieved through zoning projects. As needed, mechanical modifications and heat control can be used to obtain sufficient temperatures in the coated filters. These aspects can be done individually or in a combination.
    [31] With regard to particulate (or particle) material filters, it is typically thought that relatively small pores and / or low porosity are desirable for capturing fine particulate matter. It has been unexpectedly discovered in detailed modalities that filters of larger pore size and higher porosity can show improved filtration in the presence of a wash layer load. Not only is improved filtration achieved, but washing layer loads in higher porosity / larger pore size filters can additionally meet gas mission standards (HC, NOx and CO). Improved filtration over time in constant particle size distribution and wash layer loading is also unexpectedly achieved by the high pore filter / large pore size compared to the low pore filter / small pore size. Without wishing to be limited in theory, it is thought that low pore / small pore size filters cannot generally accommodate enough catalyst load to meet HC, NOx and CO conversion requirements due to the back pressure impact.
    [32] In one or more embodiments, the filter substrate has two (or more) average pore sizes, meaning that there can be more than one average pore size when a measurement of pore size distribution is made. Such measurements can be made on filter substrates. For example, there may be two distinct peaks present in the measurement of pore size distribution. In one embodiment, the filter has a pore size distribution such that a first average pore size is less than or equal to 30, 25, 20, 15 or even 10 μm and a second average pore size is greater than or equal at 30, 50, 70 or even 100 μm, due to an asymmetric slope of the pore size distribution.
    [33] Similarly, catalytic materials can be characterized as having two (or more) average particle sizes, which means that there may be more than one average particle size present in the catalytic material. One way to demonstrate this is by using an asymmetric particle size distribution curve. Such a curve can result from the sum of one or more monomodal distributions (that is, symmetrical). For example, there may be two distinct peaks present in a particle size distribution measurement of the catalytic material. According to certain embodiments of the present invention, the catalyst or catalytic material is provided with a particle size distribution such that a first particle size d90 is less than or equal to 7.5 μm (for example, approximately 6.5 , 6.0, 5.5, 5, 4, 3, 2 or even 1 μm) and a second d90 particle size is greater than 7.5 μm (for example, 7.6, 10, 15, 20, 30 or even 50 μm). The distribution of a catalytic material having more than one average particle size can be done in many ways such as by providing one or more wash layers having a particle size distribution of two or more average particle sizes, or by providing one or more more wash layers each having a different single or monomodal particle size distribution, or combinations thereof. In one embodiment, a wash layer having a particle size distribution such that there are two average particle sizes (d50) and / or d90 is provided. In another embodiment, two wash layers are provided, each having a different monomodal particle size distribution. An additional embodiment provides that a first wash layer has a particle size distribution of two average particle sizes (d50) and / or d90 and a second wash layer has a monomodal particle size distribution. Without claiming to be limited in theory, it is thought that the use of catalytic material having a particle size distribution with more than an average particle size will increase the coating on and in a filter that has a pore size distribution with more than an average pore size. A general pore size / porosity distribution suitable for retaining materials in fine GDI engine particles while still providing catalytic treatment of emissions can then be provided without sacrificing back pressure.
    [34] Reference to “full TWC functionality” means that oxidation of HC and CO and NOx reduction can be obtained in accordance with requirements of regulatory bodies and / or car manufacturers. Thus, platinum group metal components such as platinum, palladium and rhodium are provided to obtain conversions from HC, CO and NOX and sufficient oxygen storage components (OSC) are provided to obtain sufficient oxygen storage capacity to ensure conversion HC, NOx and CO in an environment of variable A / F ratios (air to fuel). Sufficient oxygen storage capacity generally means that after an aging full life as defined by a car manufacturer, the catalyst can store and release a minimum amount of oxygen. In one example, a useful oxygen storage capacity may be 100 mg per liter of oxygen. For another example, a sufficient oxygen storage capacity can be 200 mg per liter of oxygen after 80 hours of exothermic aging at 1050 ° C. Sufficient oxygen storage capacity is required to ensure that on-board diagnostic (OBD) systems detect a functioning catalyst. In the absence of sufficient oxygen storage capacity, the OBD will trigger an alarm for a catalyst not in operation. High oxygen storage capacity is more than enough, which expands the catalyst's operational window and allows more flexibility in engine control for a car manufacturer.
    [35] Oxygen storage component (OSC) reference refers to an entity that has been in a multi-valence state and can actively react with oxidants such as nitrous oxides or oxygen under oxidative conditions, or reagent with reducing media such as carbon monoxide (CO) or hydrogen under reducing conditions. Examples of suitable oxygen storage components include cerium. Praseodymium can also be included as an OSC. The distribution of an OSC to the wash layer can be achieved by using, for example, mixed oxides. For example, cerium can be supplied by a mixed oxide of cerium and zirconium, and / or a mixed oxide of cerium, zirconium and neodymium. For example, praseodymium can be supplied by a mixed oxide of praseodymium and zirconium, and / or a mixed oxide of praseodymium, cerium, lanthanum, yttrium, zirconium and neodymium.
    [36] Before describing several exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process steps set out in the description below. The invention is capable of other modalities and can be put into practice or carried out in various ways.
    [37] Returning to figure 1, an emission treatment system 3 comprises a gasoline engine 5 that carries exhaust through line 7 to an optional first TWC catalyst 9. In some cases the first TWC catalyst may be less than otherwise required due to a TWC-coated particulate material filter downstream 13, which receives the discharge flow through line 11. In cases where the TWC 13-coated particulate material filter provides full TWC functionality, the first TWC it may not be necessary. Line 15 can lead to additional treatment components and / or the tail pipe and out of the system. In other cases, the TWC 13 coated particulate filter contains a TWC catalyst filler that is designed to work in combination with the first TWC catalyst to meet emission requirements.
    [38] Figure 2 represents an integrated emission treatment system 30 comprising a TWC catalyst section 32, a particulate material filter section 34, an optional NOx collector 36 and SCR 38. During the treatment of a flow exhaust gas emission exhaust gas flows from an engine through the integrated emission treatment system 30 for the treatment and / or conversion of exhaust gas emission contaminants such as unburned hydrocarbons (HC), carbon monoxide ( CO), nitrogen oxides (NOx) and particulate material. The exhaust gas flows sequentially through the upstream TWC catalyst section 32, a particulate material filter section 34, an optional NOx collector 36 and SCR catalyst 38. In an alternative integrated system, the TWC catalyst can be coated over the particulate material filter, thereby eliminating a section.
    [39] TWC catalysts that have good activity and long life comprise one or more metals in the platinum group (eg platinum, palladium, rhodium, rhenium and iridium) disposed on a raised surface area, supported by refractory metal oxide, for example example, a high surface area alumina coating. The support is loaded on an appropriate carrier or substrate such as a monolithic carrier comprising a refractory metal or ceramic honeycomb structure, or refractory particles such as spheres or short extruded segments of an appropriate refractory material. Refractory metal oxide supports can be stabilized against thermal degradation by materials such as zirconia, titania, alkaline earth metal oxides such as barium, calcium or strontium or more commonly, rare earth metal oxides, for example cerium, lanthanum and mixtures of two or more oxides of rare earth metal. For example, see US patent 4,171,288 (Keith). TWC catalysts can also be formulated to include an oxygen storage component.
    [40] Reference to a “support” in a catalyst wash layer layer refers to a material that receives precious metals, stabilizers, promoters, binders and the like through association, dispersion, impregnation or other appropriate methods. Examples of supports include, but are not limited to, high surface area refractory metal oxides and composites containing oxygen storage components. High surface refractory metal oxide supports refer to support particles having pores larger than 20 Â and a wide pore distribution. High surface area refractory metal oxide supports, for example, alumina support materials, also referred to as “gamma alumina” or “activated alumina”, typically have a BET surface area in excess of 60 square meters per gram (“m2 / g ”), often up to approximately 200 m2 / g or higher. Such activated alumina is usually a mixture of the gamma and delta phases of alumina, but it can also contain substantial amounts of eta, cover and theta alumina phases. Refractory metal oxides other than activated alumina can be used to support at least some of the catalytic components in a given catalyst. For example, bulk cerium, zirconia, alpha alumina and other materials are known for such use. Although many of these materials have the disadvantage of having a considerably lower BET surface area than activated alumina, this disadvantage tends to be offset by increased durability of the resulting catalyst. “BET surface area” has its normal meaning of referring to the Brunauer, Emmett, Teller method to determine surface area by N2 adsorption.
    [41] One or more embodiments include a high surface area refractory metal oxide support comprising an activated compound selected from the group consisting of alumina, alumina-zirconia, alumina-ceria-zirconia, lanthanum-alumina, lanthanum-zirconia-alumina , barium-alumina, lanthanum-alumina barium, lanthanum-neodymium barium alumina, and alumina- Examples of composites containing oxygen storage components include, but are not limited to, ceria-zirconia and ceria-zirconia-lanthanum. Reference to a “ceria-zirconia composite” means a composite comprising cerium and zirconia, without specifying the quantity of any component. Cerium-zirconia composites include, but are not limited to, composites having, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55 %, 60%, 65%, 70%, 75%, 80%, 85%, 90% or even 95% cerium content. Certain modalities provide that the support comprises bulk ceria having a nominal ceria content of 100% (ie> 99% purity). In one or more embodiments, the support material is substantially free of alumina to maximize the oxygen storage capacity of the catalyst. Reference to "substantially free of alumina" means that alumina is present in an amount not greater than 5% of the total charge of the catalytic material. As desired, the catalytic material can be completely free of alumina, that is, it can be free of alumina.
    [42] As used here, molecular sieves, such as zeolites, refer to materials, which can in particulate form support metals of the precious catalytic group, materials having a substantially uniform pore distribution with the average pore size not being greater than than 20 Â. reference to a “non-zeolite support” in a catalyst wash layer layer refers to a material that is not a molecular sieve or zeolite and that receives precious metals, stabilizers, promoters, binders and the like through association, dispersion, impregnation or other appropriate methods. Examples of such supports include, but are not limited to, high surface area refractory metal oxides.
    [43] Reference to “impregnated” means that a solution containing precious metal is placed in pores of a support. In detailed modalities, impregnation of precious metals is obtained by incipient moisture, where a volume containing diluted precious metal is approximately equal to the pore volume of the support bodies. Impregnation of incipient moisture generally leads to a substantially uniform distribution of the precursor solution throughout the support pore system. Reference to “close contact” includes having an effective amount of components in such contact (eg, Pd and OSC) on the same support, in direct contact, and / or in substantial proximity such that OSC contacts oxygen components before the component Pd.
    [44] The TWC catalytic material may comprise a first wash layer comprising a platinum group metal and an oxygen storage component composite material. Optionally, the filter can be coated before any washing layer containing metal from the platinum group with a lower washing layer comprising cerium and optionally a stabilizer selected from the group consisting of lanthanum, zirconium, praseodymium, yttrium and neodymium. The oxygen storage component can be preset in an amount ranging from 0.5 to 4.0 g / in3 (30.5 g / L to 244 g / L). One embodiment provides the TWC catalytic material and is substantially free of alumina. Another embodiment provides that the TWC catalytic material is free of NOx-retaining components. Yet another embodiment, the TWC catalytic material stores at least 200 mg / L of oxygen after an aging of the total useful life.
    [45] In a zone mode, the catalyzed particulate material filter comprises an upstream zone and a downstream zone that both comprise a palladium component, where the upstream zone comprises the palladium component in an amount that is greater than the amount of the palladium component in the downstream zone. An example provides that there is 20 - 100 g / ft3 (0.7 to 3.5 g / L) of palladium in the upstream zone and 1 - 20 g / ft3 for the downstream zone. Particulate material collector
    [46] Reference to a particulate material collector means a filter so dimensioned and configured to retain particulate materials generated by the combustion reactions in the direct injection gasoline engine. The retention of particulate materials can occur, for example, through the use of a particulate material filter (or soot), through the use of a direct flow substrate having a tortuous internal path such that a change in the flow direction of the particulate materials cause them to fall out of the discharge stream, by using a metallic substrate, such as a corrugated metal carrier or by other methods known to those skilled in the art. Other filter devices may be appropriate, such as a pipe with a rough surface that can push particles out of the discharge stream. A tube with a curve can also be appropriate.
    [47] With reference to filters, figure 3 represents a perspective view of an exemplary wall flow filter substrate suitable for a particulate material filter. Wall flow substrates useful for supporting the oxidation catalyst or TWC compositions have a plurality of substantially parallel, thin gas flow passages extending along the longitudinal geometric axis (or axial length) of the substrate. Typically, each passage is blocked at one end of the substrate body, with alternating passages blocked on opposite extreme faces. Such monolithic carriers can contain up to approximately 300 flow passages (or “cells”) per square inch of cross section, although a much smaller number can be used. For example, the carrier may have approximately 7 to 300, more typically approximately 200 to 300, cells per square inch ("cpsi"). The cells can have cross sections that are rectangular, square, circular, oval, triangular, hexagonal, or are of other polygonal shapes. Flow wall substrates typically have a wall thickness between 0.008 and 0.016 inch. Specific wall flow substrates have a wall thickness between 0.010 and 0.012 inch. Axial zoning may be desirable in such a way that a coating is provided over an axial length of the filter. On the entry side, as measured from the upstream end 54, a coating can extend up to 50% of the axial length (for example, 1 to 49.9% or 10 to 45%), 50 to 75% of the axial length or even 100 % of axial length. On the outlet side, as measured from downstream end 56, a coating can extend up to 50% of the axial length (for example, 1 to 49.9%, or 10 to 45%), 50 to 75% of the axial length, or even 100% of the axial length.
    [48] Figures 3 and 4 illustrate a wall flow filter substrate 50 that has a plurality of passages 52. The passages are tubularly enclosed by the inner walls 53 of the filter substrate. The substrate has an inlet end or upstream 54 and an outlet end or downstream 56. Alternating passages are fitted to the inlet end with inlet plugs 58 and the outlet end with outflow plugs 60 to form tray patterns of Opposite checkers at inlet 54 and outlet 56. A gas flow 62 enters the upstream end 54 through the non-seated channel inlet 64, is stopped by outlet plug 60 and diffuses through channel walls 53 (which are porous) to the outlet side 66. A coating on the inlet side of the filter means that the coating resides on or in the walls 53 such that the gas flow 62 contacts the inlet coating first. A coating on the outlet side of the filter means that the coating resides on or in the walls 53 such that the gas flow 62 contacts the outlet coating after the inlet coating. The gas cannot pass back to the inlet side of the walls due to inlet plugs 58.
    [49] Wall flow filter substrates can be composed of ceramic-like materials such as cordierite, alumina, silicon carbide, aluminum titanate, mullite or refractory metal. Wall flow substrates can also be formed from ceramic fiber composite materials. Specific wall flow substrates are formed from cordierite, silicon carbide and aluminum titanate. Such materials are able to resist the environment, particularly high temperatures, found in the treatment of discharge flows.
    [50] Wall flow substrates for use in the inventive system may include honeycombs with a porous, thin wall (monoliths) through which the fluid flow passes without causing an excessively large increase in back pressure or pressure through the article. Ceramic wall flow substrates used in the system can be formed from a material having a porosity of at least 40% (for example, 40 to 70%). Useful wall flow substrates can have an overall average pore size of 10 or more microns. Certain wall-flow substrates have an asymmetric pore size distribution with a first medium pore size not greater than 30 μm and a second medium pore size not greater than 30 μm. In a specific embodiment, the substrates can have a porosity of at least 55% and a first average pore size in the range of 10 to 30 microns and a second average pore size in the range of 31 to 100 microns. When substrates with these porosities and these average pore sizes are coated with the techniques described below, adequate levels of TWC compositions can be loaded onto the substrates to obtain excellent conversion efficiency of hydrocarbon, CO and / or NOx. These substrates are still capable of retaining adequate discharge flow characteristics, that is, acceptable backpressures, despite the catalyst load.
    [51] The porous wall flow filter used in this invention is a catalyst in which the wall of the element has over it or contained in it one or more catalytic materials. Catalytic materials may be present on the inlet side of the element wall alone, outlet side alone, both inlet and outlet sides, or the wall itself may consist entirely or in part of the catalytic material. The present invention includes the use of one or more layers of washing catalytic materials and combinations of one or more layers of washing catalytic materials on the walls of entry and / or exit of the element.
    [52] To coat the wall flow filters with the TWC or oxidation catalyst composition, the substrates are immersed vertically in a portion of the catalyst paste in such a way that the top of the substrate is located just above the surface of the paste. In this way, the paste contacts the entrance face of each honeycomb wall, but is prevented from contacting the exit face of each wall. The sample is left in the paste for approximately 30-60 seconds. The filter is removed from the paste, and excess paste is removed from the wall flow filter first by allowing it to drain from the channels, then by blowing with compressed air (against the direction of paste penetration), and then by pulling vacuum from the paste penetration direction. By using this technique, the catalyst paste permeates the filter walls, yet the pores are not clogged to the point that undue back pressure will accumulate in the finished filter. As used herein, the term "permeate" when used to describe the dispersion of the catalyst paste in the filter, means that the catalyst composition is dispersed throughout the filter wall.
    [53] The coated filters are typically dried at approximately 100 ° C and calcined at a higher temperature (for example, 300 to 450 ° C and up to 590 ° C). After calcining, the catalyst load can be determined by calculating the coated and uncoated weights of the filter. As will be apparent to those skilled in the art, the charge of the catalyst can be modified by altering the solids content of the coating paste. Alternatively, repeated immersions of the filter in the coating paste can be conducted, followed by removal of the excess paste as described above.
    [54] With reference to a metallic substrate, a useful substrate can be composed of one or more metals or metal alloys. Metal carriers can be used in various formats such as corrugated sheet or monolithic form. Specific metal supports include heat-resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium and / or aluminum, and the total amount of these metals may advantageously comprise at least 15% by weight of the alloy, for example, 10-25% by weight of chromium, 3-8% by weight of aluminum and up to 20% by weight of nickel. The alloys may also contain small or residual amounts of one or more other metals such as manganese, copper, vanadium, titanium and the like. The surface of the metal carriers can be oxidized at elevated temperatures, for example, 1000 ° C and higher, to improve the corrosion resistance of the alloys by forming an oxide layer on the surfaces of the carriers. Such oxidation induced by high temperature can increase the adhesion of a catalytic material to the carrier. Preparation of catalyst composite wash layers
    [55] Catalyst composites can be formed in a single layer or multiple layers. In some cases, it may be appropriate to prepare a paste of catalytic material and use that paste to form multiple layers in the carrier. Composites can be easily prepared by processes well known in the prior art. A representative process is set out below. As used here, the term “washing layer” has its normal meaning in the technique of a thin adherent coating of a catalytic or other material applied to a substrate-bearing material, such as a honeycomb carrier element, which is sufficiently porous to allow the flow of gas being treated to pass through. A "wash layer layer", therefore, is defined as a coating that is comprised of support particles. A "catalyzed wash layer layer" is a coating comprised of support particles impregnated with catalytic components.
    [56] The catalyst composite can be readily prepared in layers in a carrier. For a first layer of a specific wash layer, finely divided particles of a high surface area refractory metal oxide such as alumina gamma are formed into a paste in an appropriate vehicle, for example, water. To incorporate components such as precious metals (for example, palladium, rhodium, platinum, and / or combinations thereof), stabilizers and / or promoters, such components can be incorporated into the paste as a mixture of water-soluble or water-dispersible compounds or complex. Typically, when palladium is desired, the palladium component is used in the form of a compound or complex to obtain dispersion of the component in the refractory metal oxide support, for example, activated alumina. The term "palladium component" means any compound, complex or similar that, after calcination or use of it, decomposes or otherwise converts it to a catalytically active form, usually metal or metal oxide. Water-soluble compounds or water-dispersible compounds or metal component complexes can be used as long as the liquid medium used to impregnate or deposit the metal component on the refractory metal oxide support particles does not react adversely with the metal or its compound or its complex or other components that may be present in the catalyst composition and be able to be removed from the metal component by volatilization or decomposition after heating and / or applying a vacuum. In some cases, the completion of liquid removal may not occur until the catalyst is put into use and subjected to the high temperatures encountered during operation. Generically, both from the point of view of economics and environmental aspects, aqueous solutions of soluble compounds or complexes of precious metals are used. For example, suitable compounds are palladium nitrate or rhodium nitrate.
    [57] An appropriate method of preparing any layer of the layered catalyst composite of the invention is to prepare a mixture of a solution of a desired precious metal compound (for example, palladium compound) and at least one support, such as a support of refractory metal oxide, high surface area, finely divided, for example, alumina gamma, which is sufficiently dry to absorb substantially all of the solution to form a wet solid which is then combined with water to form a paste which is coated. In one or more embodiments, the pulp is acidic, for example, having a pH of approximately 2 to less than approximately 7. The pH of the pulp can be lowered by adding a suitable amount of an inorganic or organic acid to the pulp. Combinations of both can be used when the compatibility of raw materials and acid is considered. Inorganic acids include, but are not limited to, nitric acid. Organic acids include, but are not limited to, acetic, propionic, oxalic, malonic, succinic, glutamic, adipic, maleic, fumaric, phthalic, tartaric, citric and the like. Thereafter, if desired, water-soluble or water-dispersible compounds from oxygen storage components, for example, zirconium-cerium composite, a stabilizer, for example, barium acetate, and a promoter, for example, lanthanum nitrate, can be added to the folder.
    [58] In one embodiment, the slurry is further crushed to result in substantially all solids having particle sizes less than approximately 30 microns, that is, between approximately 0.1 - 15 microns, in an average diameter. The grinding can be carried out in a ball mill, circular mill, or other similar equipment, and the solids content of the paste can be, for example, approximately 20-60% by weight, more particularly approximately 30-40% by weight .
    [59] Additional layers, that is, the second and third layers can be prepared and deposited on the first layer in the same manner as described above for depositing the first layer on the carrier. Examples
    [60] The following non-limiting examples will serve to illustrate the various embodiments of the present invention. In each example, the wearer is cordierite. COMPARATIVE EXAMPLE 1
    [61] A three-way conversion catalyst (TWC) on a direct flow honeycomb substrate with a wash layer load of 1 g / in3 (61 g / L) was prepared. The direct flow substrate was 4.66 * 5 ”in size, 300/12 cpsi, 1.4 L in volume, 30 g / ft3 platinum group metals (PGM) and a PGM Pt / Pd / Rh ratio of 0 / 27/3. EXAMPLE 2
    [62] A low porosity particle filter having a three-way conversion catalyst (TWC) on the substrate wall was prepared in the wash layer loads of 1 g / in3 (61 g / L), 2 g / in3 ( 122 g / L (2 g / in3) and 3 g / in3 (183 g / L) .The filter substrate had a size of 4.66 * 5 ”, 300/12 cpsi, 1.4 L of volume 30 g / ft3metals platinum group (PGM), and a PGM Pt / Pd / Rh ratio of 0/27/3 The filter substrate had a porosity of 45% and an average pore size of 13 μm. EXAMPLE 3
    [63] A high porosity particle filter having a three-way conversion catalyst (TWC) on the substrate wall was prepared in the wash layer loads of 1 g / in3 (61 g / L), 2 g / in3 ( 122 g / L) and 3 g / inch (183 g / L). The filter substrate had a size of 4.66 * 5 ”, 300/12 cpsi, 1.4 L volume 30 g / ft3 platinum group metals (PGM), and a PGM ratio of Pt / Pd / Rh of 0 / 3/27. The filter substrate had a porosity of 65% and an average pore size of 20 μm. EXAMPLE 4
    [64] The composites of examples 1, 2 and 3 each having 1 g / in3 (61 g / L) were aged for 4 hours under hydrothermal oven aging at 900 ° C in 2% O2, 10% H2O, and the rest N2 . Under New European Drive Cycle (NEDC) conditions and a 1.6 L engine with composite located downstream of the direct gasoline injection engine in a closed coupled position, the number of particulate matter was measured using the PMP protocol (table 1 ). Emissions of non-methane hydrocarbons (NMHC), total hydrocarbons (HC), carbon monoxide (CO) and NOx were also measured (table 1).

    [65] There is significantly lower catalytic efficiency for the coated filters of examples 2 and 3 compared to comparative example 1. The comparative direct flow substrate of example 1, however, does not show filtration efficiency. The low porosity filter of example 2 in a wash layer load of 1 g / in3 (61 g / L) met the Euro 6 standard. The back pressure of examples 2 and 3 was assessed during the EUDC segment of NEDC. There was significantly higher back pressure for example 2 compared to example 3. EXAMPLE 5
    [66] The composites of example 3 in varying wash layer loads were aged for 80 hours under exothermic aging at 1000 ° C. Under New European Drive Cycle (NEDC) conditions and a 1.6 L composite engine located downstream of the direct gasoline injection engine in a closed-coupled position, the number of particulate matter was measured using the PMP protocol (Table 2a). mass emissions of particulate matter, total hydrocarbons (HC), carbon monoxide (CO), and NOx were also measured (Table 2a).

    [67] The increased wash layer load moved the high porosity filter well under the Euro 6 particulate material regulation. Particulate matter emissions from all filters easily met the Euro 6 standard. Higher wash layer reduced emissions, especially NOx. The back pressure for example 3, high porosity filter, at 2 g / in.3 load was similar to an uncoated low porosity filter as provided in example 2.
    [68] Filter substrates of 4.66 x 4.5 ”of the porosity of the charges of the high porosity filters of Example 3 were also aged for 80 hours under 1000 ° C exothermic aging and their oxygen storage capabilities were tested. Table 2b provides a summary of the data, which was calculated based on the rich / poor front / rear sensor delay time at 501 ° C / 26.1 kg / h.

    [69] Increasing the wash layer load also increases the oxygen storage capacity. EXAMPLE 6
    [70] Coated filters having 1 g / in3 (122 g / L) and 3 g / in3 (183 g / L) were combined with closed coupled TWC catalyst on a direct flow substrate having 60 g / ft3 of group metals precious. These were tested for CO2 emissions together with comparative systems having only the TWC catalyst coupled closed on a direct flow substrate (CC) or the TWC catalyst coupled closed on a direct flow substrate in combination with a TWC under the floor (UF) . The results for individual NEDC assessments on a 2.0 L engine with composite located downstream of the gasoline direct injection engine in an under-floor position are provided in Table 3.

    [71] Similar levels of CO2 emissions for closed coupled TWC catalyst in combination with coated particulate material filters compared to TWC-only catalyst systems indicated no fuel penalty under NEDC test conditions. EXAMPLE 7
    [72] The systems in Example 6, with the addition of 2 g / in3 (122 g / L) filler from Example 3, were then aged for 80 hours under 1000 ° C exothermic aging. Under New European Drive Cycle (NEDC) conditions and a 2.0 L engine with composite located downstream of the gasoline direct injection engine in a position under the floor, total hydrocarbons (HC), carbon monoxide (CO), and NOx were measured (Table 4).

    [73] The addition of TWC under the floor (UF) or coated particulate material filter allowed the system to meet Euro 6 emission standards. EXAMPLE 8
    [74] A 60 g / ft3 platinum group TWC metal catalyst system in a closed coupled position and a 3 g / pol3 coated particulate material filter was aged for 80 hours under exothermic aging at 1000 ° C and was tested under repeated NEDC tests using a 2.0 L engine. Table 5 shows particulate material numbers for the coated filter after 3 tests. This coated filter was then subjected to a regeneration activity of 15 minutes of simulated highway driving, multiple accelerations and fuel cuts having a maximum speed of ~ 130 km / h and reaching 700 ° C. The NEDC tests were then repeated 4 more times.

    [75] Table 5 indicates that the filtration efficiency of the particulate filter has improved over time. In addition, it is shown that the coated filter can be regenerated under expected road driving conditions. Emission data were also obtained that did not show an effect on HC, CO or NOx conversion after the regeneration event. EXAMPLE 9
    [76] Particulate filters coated with variable loads of example 3 were tested under repeated NEDC tests using a 2.0L engine with composite located downstream of the gasoline direct injection engine in an under floor position. Table 6 shows particulate material numbers for the coated filters.

    [77] The filtration efficiency of the high porosity filter under the floor improved as the wash layer load increased. EXAMPLE 10
    [78] A catalyzed particulate filter having a three-way conversion catalyst (TWC) on or in the substrate wall was prepared in a 2 g / in3 (122 g / L) wash layer load with variable zoning configurations. . The uncoated filter substrate had an average pore size of 20 μm and was 4.66 * 5 ”, 300/12 cpsi, 1.4 L volume. The wash layer contained 60 g / ft3 of group metals platinum (PGM), and a Pt / Pd / Rh PGM ratio of 0/57/3. Table 7 provides a summary of the washing layer of Examples 10A, 10B, and 10C and the resulting filter compared to an uncoated filter. Regarding porosity, sections of the filter were tested, including front, middle and rear portions. The middle portion was a small fraction of the general substrate. The porosity of the filter is usually obtained from an average of the porosity measurements of the front and rear portions. With respect to the particle sizes d50 and d90 mentioned for example 10C, which had an asymmetric particle size distribution, they correspond to the sum of two monomodal distributions.
    EXAMPLE 11
    [79] The catalyst filters of example 10 were aged for 80 hours under exothermic aging at 1000 ° C. Under New European Drive Cycle (NEDC) conditions and a 1.6 L engine with composite located downstream of the gasoline direct injection engine in a closed coupled position, the number of particulate matter was measured using the PMP protocol (Table 8) . Mass emissions of particulate matter, total hydrocarbons (HC), carbon monoxide (CO) and NOx were also measured (table 8). The impact of porosity on back pressure is provided in Fig. 5.

    [80] The data in Table 8 indicates that the higher porosity catalyzed filter of Example 10C having a wash layer that is coated 100% at the inlet and 100% at the outlet having two average particle sizes provides conversion of NOx, CO and Lower HC at a constant general load compared to example 10A. The filtration efficiency is also improved with the washing layer of example 10C. EXAMPLE 12
    [81] A catalyzed particulate filter having a three-way conversion catalyst (TWC) on or in the substrate wall was prepared in a wash layer load of 2 g / in3 (122 g / L) with variable zoning configurations. . The uncoated filter substrate had an average pore size of 20 μm and was 4.66 * 5 ”, 330/12 cpsi, 1.4 L in volume. The wash layer contained 60 g / ft3 of platinum group metals (PGM), and a PGM ratio of Pt / Pd / Rh of 0/57/3. Table 9 provides a summary of the washing layer of examples 12A, 12B, 12C and 12D and the resulting filter. The uncoated filter is the one shown in table 7. With regard to porosity, sections of the filter were tested, including, front, middle and rear portions. The middle portion was a small fraction of the general substrate. The porosity of the filter is usually obtained from an average of the porosity measurements of the front and rear portions. With respect to the particle sizes d50 and d90 mentioned for examples 12A, 12B, 12C and 12D, which had an asymmetric particle size distribution, they correspond to the sum of two monomodal distributions.
    EXAMPLE 13
    [82] The catalyzed filters of example 12 are aged for 80 hours under exothermic aging at 1000 ° C. under New European Drive Cycle (NEDC) conditions and a 1.6 L engine with composite located downstream of the gasoline direct injection engine in a closed coupled position, the number of particulate material is measured using the PMP protocol. Mass emissions of particulate matter, total hydrocarbons (HC), carbon monoxide (CO) and NOx are also measured. EXAMPLE 14
    [83] A particulate filter having a catalytic material is prepared using two covers: a first inlet cover and a second inlet cover. The three-way conversion catalyst (TWC) composite contains palladium in such a way that an upstream zone has more palladium than a downstream zone. The coverings are prepared as follows: First entry coverage
    [84] The components present in the first entry cover are a composite of ceria-zirconia with 45% cerium by weight and palladium. The first inlet cover is provided over the entire length of the filter. After coating, the filter plus the first inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. Second entry cover
    [85] The second inlet cover comprises palladium, which is applied as an immersion or as a wash layer paste along a length of the filter starting from the end to the downstream to form an upstream zone. After application, the filter plus the first inlet cover and second inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. EXAMPLE 15
    [86] A particle filter having a catalytic material is prepared using two covers: an inlet cover and an outlet cover. The three-way conversion catalyst (TWC) composite contains palladium and rhodium. The coverings are prepared as follows: Entrance coverage
    [87] The component present in the first entry cover is palladium, and that cover is cerium free. After coating, the filter plus the inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. Exit coverage
    [88] The outlet cover comprises rhodium and a ceria-zirconia composite with 45% cerium by weight. After application, the filter plus the inlet cover and the outlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. EXAMPLE 16
    [89] A particle filter having a catalytic material is prepared using two covers: an inlet cover and an outlet cover. The three-way conversion catalyst (TWC) composite contains palladium and rhodium. The coverings are prepared as follows: Entrance coverage
    [90] The components present in the first inlet cover are platinum and barium as a NOx retention material. After coating, the filter plus the inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. Exit coverage
    [91] The outlet cover comprises rhodium and a ceria-zirconia composite with 45% cerium by weight. After application, the filter plus the inlet cover and the outlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. EXAMPLE 17
    [92] a particle filter having a catalytic material is prepared using two covers: an inlet cover and an outlet cover. The three-way conversion catalyst (TWC) composite contains platinum and palladium. The coverings are prepared as follows: Entrance coverage
    [93] The component present in the first entry cover is palladium, and that cover is cerium free. After coating, the filter plus the inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. Exit coverage
    [94] The outlet cover comprises platinum, a ceria-zirconia composite with 45% cerium by weight, and a zeolite which is a hydrocarbon retention material. After application, the filter plus the inlet cover and the outlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. EXAMPLE 18
    [95] A particulate filter having a catalytic material is prepared using an inlet cover. The inlet cover has a bimodal particle size distribution, such that an average first particle size is 30 μm or less and a second particle size is greater than 30 μm. The particle filter has a bimodal pore size distribution, such that a first average pore size is 30 μm or less and a second pore size is greater than 30 μm. EXAMPLE 19
    [96] A particle filter having a catalytic material is prepared using two inlet covers. The first inlet cover has a first monomodal particle size distribution, with an average particle size of 30 μm or less, which is coated over 50% of the inlet from the upstream end. The second inlet cover has a second monomodal particle size distribution, with an average particle size greater than 30 μm, which is coated over the entire length of the filter. The particle filter has a bimodal pore size distribution, such that a first average pore size is 30 μm or less and a second pore size is greater than 30 μm or more. EXAMPLE 20
    [97] A particle filter from EXAMPLE 5 was additionally prepared with a second inlet cover with a third monomodal particle size distribution, with an average particle size of approximately 15 μm, which is coated over 50% of the inlet. from the upstream end. COMPARATIVE EXAMPLE 21
    [98] A particulate filter having a catalytic material is prepared using two covers: an inlet cover and an outlet cover. a three-way catalytic conversion material (TWC) is formed from a wash layer of palladium, rhodium, alumina and ceriazirconia having a monomodal particle size distribution with an average particle size of 3.5 μm. The coverings are prepared as follows: Entrance coverage
    [99] The inlet side of the filter is coated with a TWC catalytic material wash layer at a load of 0.5 g / in3. After coating, the filter plus the inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. Exit coverage
    [100] The outlet side of the filter is coated with the same wash and load layer as the inlet side. After application, the filter plus the inlet cover and the outlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. COMPARATIVE EXAMPLE 22
    [101] A particulate filter having a catalytic material is prepared using an inlet cover. The three-way conversion catalyst (TWC) composite is formed from a wash layer of palladium, rhodium, alumina and ceria-zirconia having a monomodal particle size distribution with an average particle size of 3.5 μm. The entrance cover is prepared as follows: Entrance coverage
    [102] The inlet side of the filter is coated with the TWC wash layer at a load of 1.0 g / in3. After coating, the filter plus the inlet cover are dried and then calcined at a temperature of 550 ° C for approximately 1 hour. EXAMPLE 23
    [103] A particle filter having a three-way catalytic conversion material (TWC) is prepared using an inlet cover. The inlet cover is formed by a wash layer in an amount in the range of 0.5 to 4.0 g / inch, where the wash layer comprises palladium, rhodium and ceria-zirconia. This wash layer is substantially free of alumina, such that there is only 5% alumina by weight of the total charge of catalytic material. EXAMPLE 24
    [104] A particle filter having a three-way conversion catalytic material (TWC) is prepared using two inlet covers. The first inlet cover is formed from a wash layer in an amount in the range of 0.25 to 2.0 g / inch, where the wash layer comprises palladium and a ceria-zirconia. The second inlet cover is formed by a wash layer in an amount in the range of 0.25 to 2.0 g / in3, where the wash layer comprises rhodium and a ceriazirconia that is the same or different from the ceriazirconia of the first entry cover. The two wash layers are substantially free of alumina, such that there is up to only 5% alumina by weight of the total charge of catalytic material.
    [105] Reference throughout this specification to “a modality”, “certain modalities”, “one or more modalities” or “a modality” means that a specific aspect, structure, material or characteristic described in relation to the modality is included by the least in one embodiment of the invention. In this way, the appearances of the phrases as "in one or more modalities". “In certain modalities”. “In one embodiment” in various places throughout this specification do not necessarily refer to the same embodiment as the invention. In addition, specific aspects, structures, materials or characteristics can be combined in any appropriate way in one or more modalities.
    [106] The invention has been described with specific reference to the modalities and modifications of the same as described above. Additional modifications and changes can occur to others after reading and understanding the specification. It is intended to include all these modifications and changes to the extent that they are included in the scope of the invention.
    权利要求:
    Claims (11)
    [0001]
    1. Emission treatment system downstream of a gasoline direct injection engine to treat an exhaust stream comprising hydrocarbons, carbon monoxide, nitrogen oxides and particulates, the emission treatment system comprising a catalyzed particulate filter which comprises: a three-way catalytic conversion material (TWC) which is coated over or inside a wall flow particulate filter having an uncoated porosity in the range of 55 to 70% where the catalyzed particulate filter has a coated porosity which is within 7% of the uncoated porosity of the particulate filter, characterized by the fact that the particulate filter has a pore size distribution with two distinct peaks having a first average pore size in the range of 10-30 μm and a second average pore size in the range of 31-100 μm, and the TWC catalytic material comprises a particle size distribution with two distinct peaks such that a first set of particles has a first particle size d90 in the range of 1 to 7.5 μm and a second set of particles has a second particle size d90 in the range of 7.6 μm to 100 μm.
    [0002]
    2. Emission treatment system according to claim 1, characterized by the fact that the TWC catalytic material stores at least 100 mg / L of oxygen after aging to full useful life.
    [0003]
    3. Emission treatment system according to claim 1 or 2, characterized by the fact that the uncoated porosity and the coated porosity are within 7% of each other.
    [0004]
    Emission treatment system according to any one of claims 1 to 3, characterized in that it comprises the TWC catalytic material in an amount in the range of 61 to 244 g / L (1.0 to 4.0 g / L in3).
    [0005]
    Emission treatment system according to any one of claims 1 to 4, characterized in that the catalytic material TWC comprises the second set of particulates in an amount in the range of 10-50% by weight.
    [0006]
    Emission treatment system according to any one of claims 1 to 5, characterized in that the TWC catalytic material is formed from a single washable coating composition and a single washable first coating layer is present on the side inlet along 100% of the axial length of the particulate filter and a single second washable coating layer is present on the outlet side along 100% of the axial length of the particulate filter.
    [0007]
    Emission treatment system according to any one of claims 1 to 6, characterized in that the TWC catalytic material is formed from a single washable coating composition and a single washable first coating layer is present on the side inlet along 50 to 75% of the axial length of the particulate filter from the upstream end and a single second washable coating layer is present on the outlet side, along 50 to 75% of the axial length of the filter particulate from the downstream end.
    [0008]
    8. Catalyzed particulate filter located in an emission treatment system, as defined in claim 1, characterized by the fact that the catalyzed particulate filter comprises: a three-way catalytic conversion material (TWC) that is coated on or in a particulate filter, in an amount in the range of 122 to 244 g / L (1.0 to 4 g / poP); and where the TWC catalytic material stores at least 100 mg / L of oxygen after aging at full service life and comprises an oxygen storage component in an amount in the range of 122 g / L to 244 g / L (1, 0 to 4.0 g / inch3).
    [0009]
    9. Method of treating an exhaust gas comprising hydrocarbons, carbon monoxide, nitrogen oxides and particulates, characterized by the fact that the method comprises: providing a catalyzed particulate filter comprising a three-way catalytic conversion material (TWC ) coated on or inside a particulate filter, in an amount effective to provide a number of particulate emissions of no more than 6 x 1011 per kilometer; locate the catalyzed particulate filter downstream of a direct gasoline injection engine, and contact the exhaust gas of the direct gasoline injection engine with the catalyzed particulate filter.
    [0010]
    Method according to claim 9, characterized in that it comprises providing the catalyzed particulate filter as defined in claim 8.
    [0011]
    11. Method of making a catalyzed particulate filter, characterized by the fact that the method comprises: providing a particulate filter; provide a three-way catalytic conversion material (TWC) and coat the TWC catalytic material on or inside the particulate filter in an amount of at least 61 g / L (1.0 g / in3) to form the catalyzed particulate filter such that the catalyzed particulate filter has a coated porosity that is substantially the same as an uncoated porosity of the particulate filter.
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    同族专利:
    公开号 | 公开日
    CA2796830A1|2011-10-27|
    ZA201208563B|2014-01-29|
    CN102939445A|2013-02-20|
    MY162869A|2017-07-31|
    JP2013530332A|2013-07-25|
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    法律状态:
    2018-12-26| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US32547810P| true| 2010-04-19|2010-04-19|
    US61/325,478|2010-04-19|
    US38699710P| true| 2010-09-27|2010-09-27|
    US61/386,997|2010-09-27|
    US13/087,497|2011-04-15|
    US13/087,497|US8815189B2|2010-04-19|2011-04-15|Gasoline engine emissions treatment systems having particulate filters|
    PCT/US2011/032978|WO2011133503A2|2010-04-19|2011-04-19|Gasoline engine emissions treatment systems having gasoline particulate filters|
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