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    • 专利摘要:
    treatment system for a gasoline engine exhaust gas stream, and method for treating gasoline engine exhaust gas the present invention relates to a treatment system for a gasoline engine exhaust gas stream gasoline comprising a particulate filter, said particulate filter comprising: a particulate filter substrate, an inlet layer positioned on the exhaust gas inlet surface of the filter substrate, and an outlet layer positioned on the outlet surface exhaust gas from the filter substrate, wherein the inlet layer comprises rh and / or pd, and the outlet layer comprises rh and / or a zeolite.
    公开号:BR112012002442B1
    申请号:R112012002442-6
    申请日:2010-08-05
    公开日:2019-05-28
    发明作者:Torsten Neubauer；Marcus Hilgendorff；Stephan Siemund；Alfred Helmut Punke；Gerd Grubert
    申请人:Basf Se；
    IPC主号:
    专利说明:

    “TREATMENT SYSTEM FOR A GASOLINE ENGINE EXHAUST GAS CHAIN, AND, METHOD FOR THE TREATMENT OF GASOLINE ENGINE EXHAUST GAS” TECHNICAL FIELD
    The present invention relates to a treatment system for a gasoline engine exhaust stream and a method for treating gasoline engine exhaust gas, in particular a treatment system and a method for treatment gas engine exhaust gas from gasoline direct injection engines.
    FUNDAMENTALS
    Although gasoline engines were initially operated in ways such that particulates were not formed, gasoline direct injection technologies (GDI) were later introduced that involve stratified combustion conditions resulting in under-burning conditions and improved fuel efficiency. . Such conditions, however, can lead to the generation of particulates. Particulate emissions for direct injection engines are being subject to regulations including the impending Euro 5 (September 2009) and 6 (September 2014) standards. Existing after-treatment systems for gasoline engines are not suitable to achieve the proposed particulate matter standard. In contrast to particles generated by unsatisfactory diesel burning engines, particles generated by direct gasoline injection engines tend to be finer and of smaller quantities. This is due to the different combustion conditions of a diesel engine compared to a gasoline engine. For example, the gasoline engine operates at a higher temperature than diesel engines. Thus the exhaust gas of diesel engines exhibits temperatures generally varying from 250 to 500 ° C, while the exhaust gas of gasoline engines usually have a temperature ranging from 800 to 900 ° C. Also, hydrocarbon components are different in gasoline engine emissions compared to diesel engines.
    Thus, due to the different composition and temperature of exhaust gas streams resulting from gasoline engines compared to diesel engines, in particular with respect to the much lower proportions of exhaust gas pollutants: from soot to hydrocarbon, from carbon monoxide for nitrous oxide, respectively, a different treatment concept is necessary considering both the type and the composition of the apparatus involved in the treatment of exhaust gas such as particulate filters, TWC, and NO X trappers, as well as the positioning of these components in a system adapted for the treatment of such exhaust gas streams. More specifically, although diesel engine exhaust gas streams typically contain about 0.14% by weight of total hydrocarbon, CO and NO X pollutants (ie about 1.2 g / km of hydrocarbons, about 0.3 g / km of CO, and about 0.23 g / km of NO X ) to about 0.02 - 0.07 g / km of soot, gasoline engine exhaust gas typically contains about 1.1% by weight of total hydrocarbon, CO and NO pollutants (ie about 5.2 g / km of hydrocarbons, about 1.5 g / km of CO, and about 3.4 g / km of NO X ) to about 0.0001 - 0.001 g / km of soot. Although the exhaust gas from direct gasoline injection engines typically contains slightly less hydrocarbon, CO and NO pollutants and slightly more soot (ie about 0.001 - 0.002 g / km), these proportions are still a long way from looking like diesel exhaust gas compositions. Other differences related to particle size and particle size distribution of soot particles in the diesel engine exhaust gas and gasoline engine exhaust gas streams, as well as the different temperatures of the combustion exhaust gas stream of diesel and gasoline in the respective engine types leads to completely different scenarios, so that diesel engine exhaust gas treatment technologies may not be readily applied in the technical field of gasoline engine exhaust gas treatment.
    In addition to regulations for the treatment of exhaust gas particles, emission standards for non-combustible hydrocarbon contaminants, unburned carbon monoxide and nitrogen oxide also continue to become more demanding. In order to meet these standards, catalytic converters containing a three-way conversion catalyst (jhree-way conversion, TWC) are located in the exhaust gas line of internal combustion engines. In particular, said catalyst promotes oxidation by oxygen in the exhaust gas stream of uncommitted hydrocarbons and uncommitted carbon monoxide as well as the reduction of nitrogen oxides into nitrogen.
    With respect to the treatment of diesel engine particulates and exhaust gases, the prior art generally provides an oxidation catalyst upstream of a particulate filter. A cleaning catalyst downstream of a combination of oxidation catalyst and particulate filter is provided in U.S. Patent Application No. 2007/0137187. Suitable cleaning catalysts downstream of the filter include another oxidation catalyst or a TWC catalyst located on a substrate support such as a flow monolith.
    Particulate filters used in diesel systems have been coated with, for example, soot-burning catalysts that facilitate passive soot regeneration. In addition, US Patent No. 7,229,597 provides a catalytic selective catalytic reduction (SCR) filter downstream of an oxidation catalyst for simultaneous treatment of nitrogen oxides (NO X ), particulate matter, and hydrocarbons . Furthermore, US Patent Application No. 2004/0219077 discloses a catalyzed filter in communication with a diesel engine exhaust. Positioning of catalysts on soot filters, however, leads to a gradual loss of effectiveness due to the harmful components of the diesel engine exhaust chain. Sufficient catalyst load is required to achieve the treatment goals, but this must be balanced with acceptable back pressure in the system.
    In addition to these, EP 2 042 226 A discloses a particulate filter for engines with a partially stoichiometric regime related to the air: fuel ratio of the combustion mixture. In particular, said document teaches a layered catalyst design, in which a layer containing Rh directly covers a layer containing Pd, and only the layer containing Rh additionally comprises an oxygen storage component (oxygen-storage component, OSC).
    Therefore an object of the present invention is to obtain a treatment system for a gasoline engine exhaust stream as well as to provide a gas treatment engine exhaust method for direct gasoline injection engines.
    SUMMARY
    Exhaust systems and components suitable for use in conjunction with gasoline engines, in particular those with direct injection technology, are provided to capture particulates in addition to reducing gas emissions such as hydrocarbons, nitrogen oxides, and carbon monoxides. Current after-treatment systems for such engines do not have particulate filters.
    In particular, The objective of the present invention is achieved by a treatment system for a gasoline engine exhaust gas stream comprising a particulate filter, said particulate filter comprising: a particulate filter substrate, a positioned inlet layer on the exhaust gas inlet surface of the filter substrate, and an outlet layer positioned on the exhaust gas outlet surface of the filter substrate, the inlet layer comprising Rh and / or Pd, and the layer output comprises Rh and / or a zeolite.
    Other aspects include emission treatment components located upstream and / or downstream of a particulate filter for treating gasoline engine exhaust gas streams comprising hydrocarbons, carbon monoxide, and nitrogen oxides, the nitrogen treatment system. emission additionally comprising a three-way conversion catalyst and / or a NO X trap.
    Still other aspects include methods of treating a gas comprising hydrocarbons, carbon monoxide, nitrogen oxides, and particulates, the method comprising: locating an emission treatment system upstream of a gasoline engine, preferably a direct injection gasoline engine ; provide a three-way conversion catalyst (TWC) and a particulate trap in the emission treatment system; and contact engine exhaust gas with the TWC catalyst and the particulate trap.
    Accordingly, the present invention also provides a method for treating gasoline engine exhaust gas comprising: (i) providing a treatment system in accordance with the present invention, and (ii) conducting an engine exhaust gas stream gasoline through the treatment system.
    Other embodiments of the present invention are presented in the claims.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figs. 1 and 2 respectively show a schematic cross-sectional detail of a wall flow particulate filter of the present invention, in which "inlet" designates a wall flow filter channel through which the exhaust gas stream enters the filter particulate, "outlet" designates a wall flow filter channel through which the exhaust gas stream exits the particulate filter, "CSFSubstrate" designates the particulate filter substrate, "A" designates the inlet layer, and "B" designates the output layer.
    DETAILED DESCRIPTION
    In accordance with the present invention, a treatment system is provided comprising a particulate filter that is specially adapted for the treatment of exhaust gas streams from the gasoline engine, in particular those from direct injection gasoline engines. More specifically, the particulate filter comprises a particulate filter substrate, an inlet layer on a surface of the filter substrate which, when applied for the treatment of an exhaust gas, is the first to be contacted by the incoming gas stream. , and an outlet layer positioned on a surface of the filter substrate which is the last to be contacted by the exhaust gas, after the gas stream has passed through the filter substrate.
    In principle, any filter substrate can be used in the present invention, as long as it allows for the effective filtration of the particulate matter contained in gasoline engine exhaust gas streams. Preferably, a particulate trap is used as the filter substrate, and according to the present invention, reference to a particulate trap means a filter sized and configured in such a way to trap particles generated by combustion reactions in the engine gasoline, preferably gasoline engines with direct injection technologies. Particulate trapping can occur, for example, by using a flow substrate having a tortuous internal path in such a way that a change in the flow direction of the particulates causes them to fall out of the exhaust stream, by the use of a substrate, such as a corrugated metal support, or by other methods known to those skilled in the art.
    According to a preferred embodiment, the substrate is a flow monolith, preferably a wall flow filter, and more preferably a wall flow filter having a honeycomb structure. Useful wall flow substrates include those having a plurality of thin, substantially parallel gas flow passages extending along the longitudinal axis of the substrate. Preferably, each passage is blocked at one end of the substrate body, with alternating passages blocked at opposite end faces. U.S. Patent No. 4,329,162 is incorporated herein by reference with respect to the disclosure of suitable wall flow substrates that can be used in accordance with the present invention.
    The particulate filter substrate can be designed from any material or combination of materials allowing the filtration of particulate matter contained in gasoline engine exhaust gas without impeding the function of a gasoline engine in fluid communication with the particulate filter. For this purpose, porous materials are preferably used with the substrate material, in particular ceramic-like materials such as cordierite, α-alumina, silicon carbide, aluminum titanate, silicon nitride, zirconia, mullite, spodumene, silica alumina-magnesia and zirconium silicate, as well as porous refractory metals and their oxides. According to the present invention, "refractory metal" refers to one or more metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The particulate filter substrate can also be formed from fiber and ceramic composite materials. According to the present invention, the particulate filter substrate is preferably formed from cordierite, silicon carbide, and / or aluminum titanate. In general, materials that are capable of withstanding the high temperatures to which a particulate filter is exposed when used in the treatment of exhaust gas from a gasoline engine are preferred.
    Among the preferred wall flow filter structures that can be used in particulate filters according to the present invention, those structures that exhibit thin walls in such a way that back pressure and / or pressure drop through the filter are particularly preferred. can be kept to a minimum. Although the preferred thickness of the wall flow filter structure is highly dependent on the type of material used and its porosity, the wall thickness according to the present invention preferably ranges from 10 pm to 1 mm, more preferably from 50 pm to 600 pm, more preferably from 100 pm to 400 pm, and even more preferably from 250 pm to 350 pm.
    Regarding the porosity and the average pore size of the substrate material used in the particulate filter, any porosity and average pore size can be used, as long as the particles contained in the exhaust gas of the gasoline engine can be effectively filtered from the current gaseous simultaneously not causing a back pressure and / or pressure drop that can prevent the normal operation of a gasoline engine that is preferably in fluid communication with the particulate filter. This, however, is highly dependent on the filter structure itself as well as the wall thickness on preferred wall flow filter substrates. However, according to the present invention, particulate filter substrate materials having a porosity ranging from 20% to 80% are preferred, with porosities ranging from 25% to 75% being particularly preferred. Even more preferably, the filter substrate materials according to the present invention exhibit porosities ranging from 35% to 65%, even more preferably from 40% to 60%, and even more preferably from 45% to 55%.
    Within the meaning of the present invention, the porosity of a given material is defined as the ratio of the volume of the void space to the total or mass volume of the material itself. Preferably, the porosity within the meaning of the present invention refers to the open or effective porosity of the given material as the fraction of the total volume in which the fluid flow is effectively occurring, and therefore excludes dead end pores or unconnected cavities.
    Regarding the average pore size of the porous materials contained in the particulate filter substrate according to the present invention, said materials can exhibit any conceivable average pore size and pore size distribution, provided that the particles contained in the exhaust gas gasoline engines can be effectively filtered out of the gas stream simultaneously without causing a back pressure and / or pressure drop that could impede the normal operation of a gasoline engine that is preferably in fluid communication with the particulate filter. Preferably, materials exhibiting an average pore size of 2 pm or greater are used, most preferably the average pore size ranges from 5 to 30 pm, even more preferably from 10 to 20 pm.
    Regarding the substrates of the honeycomb structure wall flow filter, said filter structures can generally exhibit any cell density, with "cell density" or "cell density" according to the present invention referring to the number of closed cells found on a filter cross-sectional surface perpendicular to the filter axis. The cells can have any conceivable cross-sectional geometry, with rectangular, square, circular, oval, triangular, hexagonal geometries, and combinations of two or more of said geometries are preferred. Preferably, wall flow filter substrates exhibiting a cell density of 10 to 200 cells per cm 2 are, more preferably 20 to 100 cells per cm 2 , more preferably 30 to cells per cm 2 , and even more preferably 40 at 55 cells per cm 2 .
    When substrates with these porosities and these average pore sizes are coated with the techniques described below, suitable levels of catalytic compositions can be loaded onto the substrates to achieve excellent hydrocarbon, CO, and / or NO X conversion efficiencies. In particular, these substrates are capable of retaining adequate exhaust flow characteristics, ie, acceptable backpressures, regardless of the catalyst load.
    In particular, according to the present invention, the particulate filter contained in the treatment system contains an inlet layer positioned on the exhaust gas inlet surface of the filter substrate. As previously described, the "inlet layer" according to the present invention designates a layer that is positioned on a surface of the filter substrate which, when applied for the treatment of an exhaust gas, is the first to be contacted by incoming gas stream. For example, as shown in Figures 1 and 2 showing a cross-section detail of a preferred wall flow particulate filter according to the present invention, the inlet layer A is positioned on the channel walls through which the Exhaust gas from the gasoline engine enters this filter during the treatment process.
    In addition to said inlet layer, the particulate filter supplied to the treatment system according to the present invention additionally comprises an outer layer, the term "outer layer" designating a layer that is positioned on the surface of the filter substrate which is the last one to be contacted by the exhaust gas, after the gas stream has passed through the filter substrate during its treatment. Thus, as shown in Figures 1 and 2 showing a cross-section detail of a wall flow particulate filter according to the present invention, the outlet layer B is positioned on the channel walls through which the flue gas exhaust of the gasoline engine leaves this filter during the treatment process.
    According to the present invention, any type of conceivable layer can be used in the particulate filter, preferably washcoat layers (covering layers with a high catalyst-supporting surface area) are used.
    In principle, the inlet and outlet layers can be positioned over the particulate filter in any conceivable way. In particular, the layers can be applied in such a way that either the entire inlet and / or outlet surface of the particulate filter is covered by the layer in question, or only a portion thereof. Within the meaning of the present invention, "inlet surface" is to be understood as a surface of the filter substrate that is the first to be contacted by an incoming gaseous stream, and "outlet surface" is to be understood as the surface of the filter substrate which is the last to be contacted by the exhaust gas, after the gas stream has passed through the filter substrate during its treatment. In this regard, it is conceivable according to the present invention, that only a portion of the inlet surface is covered by the inlet layer when the outlet surface is completely covered by the outlet layer, and, vice versa, only a portion of the the outlet surface of the filter substrate is covered by the outlet layer when the inlet surface is completely covered by the inlet layer. Preferably, however, the inlet and outlet surfaces are either completely covered or only partially covered by the respective layers as shown by way of example in Figures 1 and 2, respectively, with respect to a preferred wall flow filter substrate.
    In case the inlet or outlet surface of the filter is the only partly covered, the portion of the surface which is covered preferably ranges from 10 to 90%, more preferably from 20 to 80%, more preferably from 30 to 70%, plus preferably from 40 to 60%, and even more preferably from 45 to 55%. According to the modalities of the present invention in which only a portion of the inlet and / or outlet surface of the particulate filter is covered, it is preferred that the covered portion is located on that portion of the inlet and outlet surfaces which is the first to contact the incoming gas stream or the last to contact the gas stream having passed through the filter substrate, respectively. According to a particularly preferred embodiment of the present invention, the sum of the portion of the input surface covered by the input layer and the portion of the output surface covered by the output layer totals a percentage ranging from 50 to 150%, preferably from 60 to 140%, more preferably from 70 to 130%, more preferably from 80 to 120%, more preferably from 90 to 110%, more preferably from 95 to 105%, more preferably from 98 to 102%, more preferably from 99 to 101% , and even more preferably
    90.5 to 100.5%. By way of example, Figure 2 displays said particularly preferred embodiment for a preferred wall flow filter substrate in which 50% of the surfaces of the inlet and outlet layers are respectively covered by the inlet and outlet layers, and the portion of the Inlet and outlet surfaces respectively covered represent the first 50% of the inlet surface to be contacted by the incoming gaseous stream, and the last 50% of the outlet surface to be contacted by the gaseous stream exiting the filter substrate, respectively.
    Thus, with reference to the embodiments of the present invention in which a wall flow filter is used as the filter substrate, those comprising an inlet end, an outlet end, an axial length of substrate extending between the inlet end and outlet end, and a plurality of passages defined by the inner walls of the wall flow substrate, the plurality of passages comprising inner passages having an open inlet end and a closed outlet end, and outlet having a closed inlet end and an open outlet end, the inner walls of the inlet passages comprising a first inlet lining extending from the inlet end to a first inlet lining end, thereby defining a first inlet lining length, the first length being inlet lining is x% of the axial length of the substrate, the inner walls of the outlet passages comprising a first outlet lining extending from the outlet end to an outlet lining end, thereby defining a first length of exit coating, the first exit coating length being (100x)% of the axial length of the substrate, where 0 <x <100.
    In particularly preferred embodiments, x ranges from 25 to 75%, preferably from 35 to 65%, and more preferably from 45 to 55%.
    In addition, it has been surprisingly found that the use of specific inlet and outlet layer compositions according to the present invention washes particulate filters that can be effectively used in the treatment of exhaust gas from a gasoline engine, in particular in the treatment exhaust gas from direct injection gasoline engines. In this regard, it has surprisingly been found that specific combinations of compositions for inlet and outlet layers are particularly well suited for the treatment of gasoline engine exhaust streams.
    More specifically, combinations of the input and output layer compositions according to the present invention refer to the input layers comprising Rh, Pd, or both Rh and Pd in combination with the output layer compositions comprising Rh, a zeolite , or both Rh and a zeolite.
    Thus, the present invention relates to a treatment system for a gasoline engine exhaust gas stream comprising a particulate filter, said particulate filter comprising:
    a particulate filter substrate, an inlet layer positioned on the exhaust gas inlet surface of the filter substrate, and an outlet layer positioned on the exhaust gas outlet surface of the filter substrate, the layer being inlet comprises Rh and / or Pd, and the outlet layer comprises Rh and / or a zeolite.
    According to a preferred embodiment of the present invention, the inlet layer of the particulate filter comprises Pd, and the outlet layer comprises Rh.
    Arrangements according to the present invention are additionally preferred, in which the input layer comprises Rh and Pd, and the output layer additionally comprises Pd. Even more preferred are the modalities in which the input and output layers comprise both Rh and Pd.
    Additional preferred embodiments of the present invention are those in which the particulate filter contains an inlet layer comprising either Rh or Pd, and the outlet layer comprises a zeolite.
    Furthermore, according to a particularly preferred embodiment of the present invention, both the inlet and outlet layers of the particulate filter comprise Rh.
    According to the present invention, the inlet and / or outlet layers preferably additionally comprise Pt. Particularly preferred are the embodiments, in which the inlet and / or outlet layers additionally comprise Pt in addition to a zeolite.
    Zeolites are advantageously used in the present invention for the purpose of adsorbing hydrocarbons during the heating period of the gas engine exhaust gas treatment, when the treatment system has not yet reached the temperature required for full operation. In principle, one or more zeolites can be contained in the input layer and / or in the output layer of the particulate filter, one or more zeolites being preferably contained in the output layer. According to the particularly preferred embodiments of the present invention, the layer comprising one or more zeolites additionally comprises Pt for oxidizing the hydrocarbon adsorbed at higher temperatures.
    Generally, any conceivable zeolite can be used in the present invention, preferably a zeolite which is selected from the group consisting of faujasite, chabazite, clinoptilolite, mordenite, silicalite, zeolite X, zeolite Y, ultra-stable Y zeolite, ZSM5 zeolite is used. ZSM-12, zeolite SSZ-3, zeolite SAPO 5, ofretite, bitumen zeolite, and mixtures thereof. In particularly preferred embodiments, the zeolite is selected from the group consisting of ZSM zeolites, bitumen zeolite, Y zeolite, and mixtures thereof.
    The zeolites used in the present invention can have any conceivable proportion of Si: Al, as long as the effective treatment of gasoline engine exhaust gas can be carried out, in particular at the high temperatures involved in the treatment of gasoline engine exhaust gas. Preferably, zeolites have a Si: Al ratio ranging from 25 to 1,000, more preferably from 50 to 500, and even more preferably from 100 to 250. Alternatively, Si: Al ratios ranging from 25 to 300 are preferred, even more preferably from 35 to 180.
    In general, the inlet and outlet layers can comprise a support material, preferably a metal oxide as a support for other components contained therein, in particular for the transition metals Rh and / or Pd. However, in embodiments in which the outlet layer comprises a zeolite, said layer preferably does not further comprise a support material, in particular, when said layer does not comprise a platinum group metal. Within the meaning of the present invention, "platinum group metal" refers to a metal or combinations of two or more metals selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum.
    Reference to a "support" in a catalyst layer refers to a material that receives components such as precious metals, in particular platinum group metals, stabilizers, promoters (preferably transition metals), binders, and the like by means of association, dispersion, impregnation, or other suitable methods. Reference to "impregnated" means that the respective components are positioned on the support material, in particular inserted into the pores of a support material. In detailed modalities, impregnation is carried out by incipient wetting, in which a volume of a solution containing one or more of the components is approximately equal to the volume of pores in the support body. Impregnation by incipient wetting generally leads to a substantially uniform distribution of the solution through the support pore system. Reference to "intimate contact" includes having an effective number of components in such contact on the same support, in direct contact and / or in substantial proximity.
    As a support material, any conceivable material can be used as long as said material can effectively support at least the function of at least one transition metal which can be contained in both the inlet and outlet layer of the particulate filter accordingly. with the present invention. According to the present invention, metal oxides are preferably used as the support material, more preferably those metal oxides which are selected from the group consisting of alumina, zirconia, zirconia-alumina, barium-alumina, lantanaalumina, lantana-zirconia- alumina, and their mixtures. Among said preferred support materials, lanthanum-alumina and / or zirconia-alumina are particularly preferred.
    Among the types of alumina that can be used as a support material according to the present invention, either alone or in combination with other metal oxides, gamma-alumina is preferred. According to particularly preferred embodiments of the present invention, gamma-alumina is used which has been doped with a refractory metal and / or a metal and rare earth, more preferably with lanthanum and / or zirconium.
    According to a preferred embodiment of the present invention, lanthanum-alumina is preferably used as a support material for Pd, and zirconia-alumina is preferably used as a support material for Rh. More preferably, when Pd is supported on lanthanum-alumina, said support material contains from 2 to 10% by weight of La, even more preferably 3 to 6% by weight of La, and even more preferably from 3.5 to 4, 5% by weight of La. Furthermore, when Rh is supported on zirconiaalumina, said support material preferably contains from 5 to 35% by weight of Zr, more preferably from 10 to 30% by weight of Zr, and even more preferably from 15 to 25% by weight of Zr .
    In preferred embodiments of the present invention, the inlet layer and / or the outlet layer of the particulate filter comprises an oxygen storage component (OSC). Within the meaning of, “oxygen storage component” (OSC) refers to an entity that has multiple valence states and can actively react with oxidants such as oxygen or nitrous oxides under oxidative conditions, or react with reducers such as monoxide carbon (CO) or hydrogen under reducing conditions. According to the present invention, the OSC is preferably selected from the group consisting of zirconia, ceria, barium, lantana, praseodymia, neodymia, and mixtures thereof, more preferably from the group consisting of mixtures of ceria-zirconia, ceria-zirconia-lantana, lanthanazirconia-baria-lantana, and baria-lantana-neodymia. In particularly preferred embodiments, the oxygen storage component contained in the inner layer and / or the outer layer is ceria and / or zirconia, more preferably a ceria-zirconia composite.
    According to particularly preferred embodiments, in which the input layer comprises a ceria-zirconia composite such as an OSC, said composite preferably contains from 20 to 70% by weight, more preferably from 30 to 60% by weight, more preferably from 35 to 55% by weight, and even more preferably 40 to 50% by weight.
    Furthermore, according to particularly preferred embodiments in which the outlet layer comprises a ceriazirconia composite such as an OSC, said composite preferably contains from 2 to 20% by weight, more preferably from 5 to 15% by weight, even more preferably from 8 to 12% by weight.
    In addition to or in place of an OSC, the input layer and / or the output layer may contain a NO X trapping component, said NO X trapping component preferably being selected from the group consisting of alkali metal oxides, oxides of alkaline earth metal, rare earth metal oxides, and mixtures thereof, more preferably from the group consisting of potassium, sodium, lithium, cesium, calcium, strontium, barium, cerium, lanthanum oxides, praseodymium, neodymium, and their mixtures. In particularly preferred embodiments, the NO X trapping component is barium oxide, and / or strontium oxide, more preferably barium oxide.
    In accordance with preferred embodiments of the present invention, the treatment system for gasoline engine exhaust gas additionally comprises a TWC catalyst. In principle, any TWC catalyst can be used in the treatment system according to the present invention, provided that effective treatment of exhaust gas from the gasoline engine can be carried out. Preferably, TWC catalysts comprising Rh and / or Pd are used, more preferably those comprising Pd.
    In the treatment system of the present invention, the TWC catalyst and the particulate filter are in fluid communication, with respect to the direction in which a gasoline engine exhaust gas stream flows through the system for its treatment, the catalyst TWC can be located either upstream or downstream of the particulate filter, the positioning of the TWC catalyst upstream of the particulate filter being preferred.
    In preferred embodiments of the present invention, the TWC catalyst comprises a metal oxide support material, said support material preferably being selected from the group consisting of alumina, zirconia, zirconia-alumina, barium-alumina, lantana-alumina, lantana-zirconiaalumina , and their mixtures. In particularly preferred embodiments, the metal oxide support material is gamma-alumina.
    Preferably, the support material is doped with a rare earth element in an amount preferably ranging from 0.01 to 30% by weight, more preferably from 0.05 to 15% by weight, even more preferably from 0.1 to 10% % by weight. In particular, the rare earth element is preferably selected from the group consisting of cerium, lanthanum, praseodymium, neodymium, and mixtures thereof, with the rare earth element being preferably cerium and / or lanthanum, more preferably cerium.
    According to a particularly preferred embodiment of the present invention, the metal oxide support material is gamma-alumina which is preferably doped with a refractory metal and / or a rare earth metal, more preferably with lanthanum and / or zirconium.
    In addition to or in place of said support material, the TWC catalyst according to the present invention preferably comprises an OSC, said OSC preferably being selected from the group consisting of zirconia, ceria, barium, lantana, praseodymia, neodymia, and mixtures thereof , more preferably from the group consisting of mixtures of ceriazirconia, ceria-zirconia-lantana, lantana-zirconia, baria-lantana, and bárialantana-neodymia. In particularly preferred embodiments, the OSC is ceria and / or zirconia, preferably ceria.
    According to the present invention, the treatment system may additionally comprise, in addition to or in place of a TWC catalyst, a NO X trap. WO 2008/067375 is hereby incorporated by reference with respect to the disclosure of suitable NO X captors that can be used in accordance with the present invention.
    In the treatment system of the present invention, however, it is preferred that, alternatively, either a TWC catalyst or a NO X trap is used in addition to the particulate filter. In principle, in preferred embodiments of the invention the treatment system comprising a NO x imprisoning any imprisoning of NO X can be used, provided that effective treatment of engine exhaust gas of gasoline can be performed.
    In the preferred treatment systems of the present invention, the NO X trap and the particulate filter are in fluid communication, with respect to the direction in which a gasoline engine exhaust gas stream flows through the system for its treatment , the NO X trapper can be located either upstream or downstream of the particulate filter, the position of the NO X trapper upstream of the particulate filter being preferred.
    According to a preferred embodiment of the present invention, the NO X trapper comprises a compound selected from the group consisting of alkali metal, alkaline earth metal, and rare earth metal oxides, and mixtures thereof, said compound being preferably selected of the group consisting of potassium, sodium, lithium, cesium, calcium, strontium, barium, cerium, lanthanum, praseodymium, neodymium oxides, and mixtures thereof. In particularly preferred embodiments, the NO X trapper comprises barium oxide and / or strontium oxide, more preferably barium oxide.
    In particularly preferred treatment systems of the present invention, the NO X trapper additionally comprises Pd, preferably Pd, Pt, and Rh.
    According to particularly preferred embodiments of the present invention, the function of the TWC catalyst and / or the NO X trap is adapted to the function of the particulate filter. Thus, it has been surprisingly found that the specific processes for the treatment of exhaust gas from the gasoline engine can be advantageously divided between the particulate filter and the TWC catalyst and / or the NO X trap. More specifically, it has been found quite surprisingly that when the particulate trapper comprises Rh, the NO X process for the treatment of exhaust gas from a gasoline engine mainly takes place in the particulate filter instead of in the TWC catalyst and / or in the NO X trapper . This has the considerable advantage that the volume of TWC catalyst can be reduced, thus leading to gasoline engine exhaust gas treatment systems that are highly cost efficient because the total amount of expensive metals in the platinum group can be reduced used in them, and in particular the total amount of Rh, Pd, and Pt insofar as these metals are present in particular embodiments of the present invention.
    Thus, according to a particularly preferred embodiment of the present invention, the particulate filter comprises Rh, more preferably in both the inlet and outlet layers of the particulate filter. Preferably, according to said particularly preferred embodiment, the particulate filter substantially does not contain Pd.
    Furthermore, it has been surprisingly found that when the particulate filter comprises Rh, it is advantageous that the catalyst
    TWC and / or the NO X trapper comprises Pd. In particular, since the Pd charge in a gasoline engine exhaust gas treatment system according to the present invention is preferably greater than the total Rh charge, it is advantageous that the TWC catalyst and / or the trap 10 NO X comprise Pd because better dispersion of Pd can be achieved in the same, respectively, compared to the particulate filter. Thus, in preferred embodiments of the present invention in which the inlet layer and / or the outlet layer of the particulate filter is a washcoat layer, the total volume of said layers is usually less than the volume available for the dispersion of particles. Pd and possibly other metals of the platinum group in the TWC catalyst and / or in the NO X trap. As a result, greater efficiency is achieved when the particulate filter comprises Rh and the TWC catalyst and / or the NO X trapper of the treatment system comprises Pd. Preferably, the treatment system 20 comprises a TWC catalyst comprising Pd.
    Consequently, in a particularly preferred embodiment of the present invention, the particulate filter comprises Rh and a TWC catalyst and / or a NO X trapper contained in the treatment system comprise Pd, with treatment system 25 preferably comprising a TWC catalyst comprising Pd.
    The gasoline engine exhaust gas treatment system can additionally comprise a gasoline engine, in which the exhaust gas outlet of said gasoline engine is in fluid communication with the particulate filter. Preferably, the gasoline engine is a direct gasoline injection engine.
    According to a preferred embodiment, the gasoline engine exhaust treatment system comprising a gasoline engine additionally comprises an exhaust gas duct in fluid communication with the exhaust gas outlet of the gasoline engine, the filter being particulates are positioned in said exhaust gas duct. Preferably, a TWC catalyst and / or a NO X trap is also positioned in the exhaust gas line. According to particularly preferred embodiments, the TWC catalyst and / or NO X trap are respectively located upstream of the particulate filter in the exhaust gas conduit with respect to the direction of the exhaust gas flow.
    Thus, the present invention also relates to a treatment system for a gasoline engine exhaust gas stream, said system additionally comprising: a gasoline engine, preferably a direct gasoline injection engine, and a gas duct exhaust in fluid communication with the engine, the particulate filter substrate and the optional TWC catalyst and / or NO X trap are positioned inside the exhaust gas duct.
    In addition to these, the treatment system according to the present invention can comprise other components that can be advantageously used in the treatment of exhaust gas from a gasoline engine such as one or more gas sensors and / or a gas diagnostic system board (pn-board diagnostic, OBD).
    According to another aspect of the present invention, a method is provided for treating gasoline engine exhaust gas using the gasoline engine exhaust gas treatment system as described above. In particular, a method is provided for the treatment of exhaust gas from a gasoline engine exhibiting specific amounts of hydrocarbons (HC), CO, NO X , and soot as exhaust pollutants, in particular with respect to the proportions of HC, CO, NO X , and soot produced by the combustion of hydrocarbons in gasoline engines, preferably with respect to the proportions produced by gasoline direct injection engines.
    Thus, the present invention also relates to a method for treating gas engine exhaust gas comprising:
    (i) providing a treatment system according to any of the modalities, and (ii) conducting a gasoline engine exhaust gas stream through the treatment system.
    In general, the method according to the present invention can be applied to any gasoline engine exhaust gas. Preferably, a treatment method according to the present invention is provided which uses exhaust gas from direct gasoline injection engines. Regarding the gasoline engine exhaust gas composition used in the treatment method of the present invention, the weight proportions of the pollutants HC, CO, NO X , and soot, ie in terms of the weight proportions of HC: CO: NO X : soot, preferably range from (2.5 - 7.0): (0.5 - 3.0): (1.0 - 4.7): (0.00005 - 0.01), more preferably from (3.0 - 6.8): (0.7 - 2.5): (2.0 - 4.2): (0.0001 - 0.007), more preferably (3.5 - 6.5) : (0.8 - 2.0): (2.5 - 4.0): (0.0003 - 0.005), more preferably (4.0 - 6.0): (1.0 - 1.9 ): (3.1 - 3.7): (0.0005 - 0.003), and even more preferably (4.5 - 5.5): (1.2 - 1.7): (3.2 - 3.6): (0.001 -0.0025).
    According to the method of the present invention, the temperature at which the gasoline exhaust gas stream is conducted through the treatment system, and in particular the temperature of the exhaust gas stream immediately before it comes into contact with the particulate filter usually ranges from 300 to 1,100 ° C. Preferably, the temperature of the exhaust gas stream immediately before it comes into contact with the particulate filter ranges from 450 to 1,000 ° C, more preferably from 550 to 950 ° C, more preferably from 650 to 900 ° C, and further more preferably from 750 to 850 ° C. Alternatively, the temperature of the exhaust gas stream immediately before it comes into contact with the particulate filter preferably ranges from 500 to 900 ° C, more preferably from 550 to 800 ° C, and even more preferably from 600 to 750 ° C .
    In general, any conceivable methods can be used to produce the treatment system according to the present invention. Typically, to coat the particulate filter substrate such as the preferred honeycomb structure wall flow substrates with the composition of the inlet and outlet layers, the substrates are immersed vertically in a portion of a slurry comprising the desired components, such that the top of the substrate is located immediately above the surface of the slurry. In this way the slurry contacts the entrance face of each honeycomb structure wall, but contact with the exit face of each wall is avoided. The sample is typically left inside the slurry for about 30 seconds. The substrate is then removed from the slurry, and excess slurry is removed from the wall flow substrate first by allowing it to drain from the channels, then by blowing with compressed air (against the direction of penetration of the slurry), and then by vacuum aspiration in the direction of penetration of the slurry. By using this technique, the catalyst slurry permeates the substrate walls, yet the pores are not occluded to the extent that undue pressure will form on the finished substrate. As used herein, the term "permeate" when used to describe the dispersion of the catalyst slurry over the substrate, means that the catalyst composition is dispersed throughout the substrate wall.
    The coated substrates are typically dried at about 100 ° C and calcined at a higher temperature (e.g., 300 to 450 ° C and up to 550 ° C). After calcination, the catalyst load can be determined by calculating the coated and uncoated weights of the substrate. As will be apparent to those skilled in the art, the catalyst charge can be modified by changing the solids content of the coating slurry. Alternatively, repeated immersion of the substrate into the coating slurry can be conducted, followed by removing the excess slurry as described above.
    With reference to a substrate, a useful substrate can be of a metallic nature and be composed of one or more metals or metal alloys. Metal supports can be used in various forms such as monolithic or thin corrugated sheet. Specific metal supports 15 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 can contain one or more of nickel, chromium and / or aluminum, and the total amount of these metals can advantageously contain at least 15% by weight of the alloy, eg, 10-25% by weight of chromium, 320 8% by weight aluminum and up to 20% nickel by weight. The alloys can also contain small amounts or trace amounts of one or more other metals such as manganese, copper, vanadium, titanium and the like. The surface of the metal supports can be oxidized at high temperatures, e.g., 1000 ° C and higher, to improve the corrosion resistance of the alloys by forming an oxide layer on the surfaces of the supports. Such oxidation induced by high temperature can intensify the adhesion of a catalytic material on the support.
    The catalyst composites of the present invention can be made into a single layer or multiple layers. In some situations, it may be appropriate to prepare a slurry of catalytic material and use this slurry to form multiple layers on the support. Composites can be readily prepared by processes well known in the art. A representative process is described below. As used herein, the term “washcoat” has its usual meaning in the art of an adherent, thin coating, of a catalytic material or other material applied to a substrate support material, such as a honeycomb support member, which is sufficiently porous to allow the gas stream being treated to pass through.
    The catalyst composite can be readily prepared in layers on a support. For a first layer of a specific washcoat, finely divided particles of a high surface area metal oxide such as gamma-alumina are slurried in an appropriate vehicle, e.g., water. To incorporate components such as precious metals and / or the platinum group (eg, palladium, rhodium, platinum, and / or combinations thereof), stabilizers and / or promoters, such components can be incorporated into the slurry as a mixture of compounds or water-soluble or dispersible complexes. Typically, when palladium is included in the washcoat, the palladium component is used in the form of a compound or complex to effect the dispersion of the component on the metal oxide support, e.g., activated alumina. For the purposes of the present invention, the term "palladium component" means any compound, complex, or the like that, under calcination or its use, decomposes or differently converts to a catalytically active form, usually metal or metal oxide. This applies accordingly to all elements of the platinum group used alone or in combination with each other according to the present invention. Water-soluble compounds or water-dispersible compounds or complexes of the metal component may be used provided that 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 is capable of being removed from the metal component by volatilization or decomposition by heating and / or applying a vacuum. In some cases, the complete removal of the liquid may not occur until the catalyst is put into use and subjected to the high temperatures encountered during operation. Generally, 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.
    A suitable method of preparing any layer of the layered catalyst composite of the invention is to prepare a mixture of a solution of a compound of the platinum group (eg palladium compound) and / or precious metal and at least one support, such as a finely divided, high surface area metal oxide support, eg, gamma alumina, which is dry enough to absorb the entire solution to form a wet solid which is later combined with water to form a coatable slurry. In one or more embodiments, the slurry is acidic, for example, having a pH of about 2 to less than about 7. The pH of the slurry can be lowered by adding an appropriate amount of an inorganic acid or organic in the slurry. Combinations of both can be used when compatibility of acid and raw materials is considered. Inorganic acids include, but are not limited to, nitric acid. Organic acids include, but are not limited to, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tartaric acid, citric acid and the like. Then, if desired, water-soluble or water-dispersible compounds from oxygen storage components, eg, cerium-zirconium composite, a stabilizer, eg, barium acetate, and a promoter, eg, lanthanum nitrate, can be added in the slurry.
    In one embodiment, the slurry is then comminuted to result in substantially all solids having average particle sizes of about 20 micrometers or less, preferably about 0.1 to 15 micrometers, in an average diameter. Comminution can be carried out in a ball mill or other similar equipment, and the slurry solids content can be within the range of about 20 to 60% by weight, more particularly about 30 to 40% by weight.
    Additional layers, i.e., the second and third layers can be prepared and deposited on the first layer in the same manner as described for depositing the first layer on the support.
    Examples
    Examples of particulate filters according to the present invention were prepared according to the following procedures. In all examples, a cordierite wall flow filter substrate was obtained. In the wall flow filter, alternating ends of the substantially parallel gas flow passages extending along the longitudinal axis of the substrate have been blocked both at the entrance and the exit of the monolith, such that inlet channels with an open inlet side and a blocked exit side, and exit channels with a blocked entrance side and an open exit side were formed respectively. In the following examples, layers of washcoat formed on the walls of the inner channels are designated as inlet layers and layers of washcoat formed on the walls of the outlet channels are designated as outlet layers. During operation in a treatment system according to the present invention, the particulate filter is positioned in an exhaust gas stream of the gasoline engine in such a way that the exhaust gas enters the inlet channels and, after first flowing through of the inlet layer, followed by the porous substrate material, and finally by the outlet layer, exit the particulate filter via the outlet channels.
    Example 1
    A particulate filter catalyzed by applying respective washcoat layers to the inlet and outlet channels of a cordierite wall flow filter substrate was prepared. The substrate had a volume of 85.23 in 3 (1,396.67 cm 3 ), a cell density of 300 cells per square inch (46.5 cells per cm) and a wall thickness of approximately 12 mil (0.3 mm). The final catalyzed particulate filter contained Pd and Rh with a total precious metal charge of 15 g / ft 3 (529.72 g / m 3 ) and a Pd: Rh ratio of 13.5: 1.5. In addition, the final catalyzed particulate filter had an oxygen storage component (OSC) content of 50% by weight, the inlet layer having an OSC content of 63% by weight, and the outlet layer having a content of CSO of 27%.
    The washcoat layers were prepared as follows:
    Input washcoat layer
    The components present in the entrance coating were gamma-alumina stabilized with 4% by weight of lanthanum, a composite of ceria-zirconia with 45% by weight of ceria, and barium oxide, in respective concentrations of approximately 30%, 63%, and 6% based on the weight of the incoming washcoat layer on the final calcined catalyzed particulate filter. The total load of the incoming washcoat layer on the final calcined catalyzed particulate filter was 0.5 g / in 3 (0.0305 g / cm 3 ).
    To form the entrance coating, a palladium nitrate solution was impregnated by a planetary mixer (planetary mixer, Pmixer, P-mixer) on the stabilized gamma-alumina to form a wet powder while incipient wetting was achieved, the amount of Pd was chosen in such a way that a final particulate filter concentration of 13.5 g / ft 3 (477 g / m 3 ) of Pd was achieved. An aqueous slurry was then formed by mixing all the above-mentioned components of the yvashcoat inlet layer with water, with barium oxide being supplied in the form of a barium acetate solution. The aqueous slurry was then ground to achieve a particle size distribution, in which 90% of the particles have a particle size less than 10 μιη. The slurry was then coated over the inner channels of the wall flow filter substrate using deposition methods known in the art. The coated support was then calcined at 500 ° C per hour.
    Outlet washcoat layer
    The components present in the outlet coating were gamma-alumina doped with 20% by weight of zirconium, a composite of ceriazirconia with 10% by weight of ceria, zirconium oxide, and barium oxide, in respective concentrations of 66%, 27% , 3%, and 3%, based on the weight of the outlet washcoat layer on the final calcined catalyzed particulate filter. The total loading of the outlet washcoat layer on the final calcined catalyzed particulate filter was 0.5 g / in (0.0305 g / cm).
    To form the outlet coating, a rhodium nitrate solution was impregnated by a planetary mixer (P-mixer) on the stabilized alumina to form a wet powder while incipient wetting was achieved, the amount of Rh being chosen in such a way that a final concentration in the particulate filter of
    1.5 g / ft 3 (53 g / m 3 ) of Rh. an aqueous slurry was then formed by mixing all the above-mentioned components of the yvashcoat outlet layer with water, with barium oxide being provided in the form of an aqueous barium acetate solution. the aqueous slurry was then ground to achieve a particle size distribution, in which 90% of the particles have a particle size less than 10 pm. The slurry was then coated over the outlet channels of the wall flow filter substrate using deposition methods known in the art. The coated support was then calcined at 550 ° C for 1 h, thus giving a catalyzed particulate filter.
    Example 2
    A catalyzed particulate filter was prepared by applying respective layers of yvashcoat to the inlet and outlet channels of a cordierite wall flow filter substrate. The substrate had a volume of 85.23 in 3 (1,396.67 cm 3 ), a cell density of 300 cells per square inch (46.5 cells per cm) and a wall thickness of approximately 12 mil (0.3 mm). The final catalyzed particulate filter contained Pd with a charge of 13.5 g / ft 3 (476.75 g / m 3 ).
    The yvashcoat layers were prepared as follows:
    Input yvashcoat layer
    The components present in the entrance coating were gamma-alumina stabilized with 4% by weight of lanthanum, a composite of ceria-zirconia with 45% by weight cerium, and barium oxide, in respective concentrations of approximately 30%, 63%, and 6% based on the weight of the input yvashcoat layer in the final calcined catalyzed particulate filter. The total load of the input yvashcoat layer on the final calcined catalyzed particulate filter was 0.5 g / in 3 (0.0305 g / cm 3 ).
    To form the inner lining, a palladium nitrate solution was impregnated by a planetary mixer (P-mixer) on the stabilized gamma-alumina to form a wet powder while incipient wetting was achieved, and the amount of Pd was chosen in such a way. so that a final concentration in the particulate filter of
    13.5 g / ft 3 of Pd. An aqueous slurry was then formed by mixing all the above-mentioned components of the yvashcoat inlet layer with water, with barium oxide being supplied in the form of an aqueous barium acetate solution. the aqueous slurry was then ground to achieve a particle size distribution, in which 90% of the particles have a particle size less than 10 μηι. The slurry was then coated over the inlet channels of the wall flow filter substrate using deposition methods known in the art. The coated support was then calcined at 500 ° C for 1 h.
    Outlet washcoat layer
    Zeolite Η-Bitumen, distilled water and acetic acid are mixed to obtain a solid content of 35% by weight and a pH within the range of 3 to 4. The slurry was then ground to obtain an average particle size of 5 pm . Subsequently, the slurry is applied to the outlet layer using deposition methods known in the art to obtain an outlet washcoat load on the final calcined catalyzed particulate filter of 0.2 to 0.5 g / in 3 (0.0122 at 0.0305 g / cm 3 ).
    Example 3
    A catalyzed particulate filter was prepared by applying respective washcoat layers to the inlet and outlet channels of a cordierite wall flow filter substrate. The substrate had a volume of 85.23 in (1,396.67 cm), a cell density of 300 cells per square inch (46.5 cells per cm 2 ) and a wall thickness of approximately 12 mil (0.3 mm) . The final catalyzed particulate filter contained Pd and Rh with a total precious metal charge of 15 g / ft 3 (529.72 g / m 3 ) and a Pd: Rh ratio of 13.5: 1.5.
    The washcoat layers were prepared as follows:
    Input washcoat layer
    The components present in the entrance coating were gamma-alumina stabilized with 4% by weight of lanthanum, gamma-alumina doped with 20% by weight of zirconium, a ceria-zirconia composite with
    45% by weight cerium, and barium oxide, in respective concentrations of approximately 24%, 6%, 63%, and 6% based on the weight of the incoming washcoat layer on the final calcined catalyzed particulate filter. The total load of the incoming washcoat layer on the final calcined catalyzed particulate filter was 0.5 g / in (0.0305 g / cm).
    To form the inner lining, a palladium nitrate solution was impregnated by a planetary mixer (P-mixer) on the lanthanum-stabilized gamma-alumina to form a wet powder while incipient wetting was achieved, with the amount of Pd being chosen in such a way that a final concentration in the particulate filter of 13.5 g / ft 3 (477 g / m 3 ) of Pd was reached. Subsequently, a rhodium nitrate solution was impregnated by a planetary mixer (P mixer) on the zirconium-stabilized gamma-alumina to form a wet powder while incipient wetting was achieved, the amount of Rh being chosen in such a way that it was A final concentration in the particulate filter of 1.5 g / ft (53 g / m) of Rh is achieved.
    An aqueous slurry was then formed by mixing all the above-mentioned components of the washcoat inlet layer with water, with barium oxide being supplied in the form of an aqueous barium acetate solution. The aqueous slurry was then ground to achieve a particle size distribution, in which 90% of the particles have a particle size less than 10 pm. The slurry was then coated over the inlet channels of the wall flow filter substrate using deposition methods known in the art. The coated support was then calcined at 550 ° C for 1 h.
    Outlet washcoat layer
    Zeolite Η-Bitumen, distilled water and acetic acid are mixed to obtain a slurry with a solid content of 35% by weight and a pH within the range of 3 to 4. The slurry was then ground to obtain a particle size average of 5 pm. Subsequently, the slurry is applied to the outlet layer using deposition methods known in the art to obtain an outlet washcoat load on the final calcined catalyzed particulate filter of 0.2 to 0.5 g / in (0.0122 to 5 0.0305 g / cm 3 ).
    权利要求:
    Claims (15)
    [1]
    1. Treatment system for a gasoline engine exhaust gas stream, characterized by the fact that it comprises a particulate filter, said particulate filter comprising:
    a particulate filter substrate, an inlet layer positioned on the exhaust substrate of the filter substrate, and an outlet layer positioned on the exhaust substrate of the filter substrate, wherein the layer input comprises Rh and / or Pd, and the output layer comprises Rh and / or a zeolite, and wherein said system further comprises a three-way conversion catalyst (TWC) and / or a NOx trap which is in fluid communication with the particulate filter.
    [2]
    Treatment system according to claim 1, characterized in that when the input layer comprises Rh and Pd, the output layer additionally comprises Pd.
    [3]
    3. Treatment system according to claim 1 or 2, characterized by the fact that zeolite is selected from the group consisting of faujasite, chabazite, clinoptilolite, mordenite, silicalite, zeolite X, zeolite Y, ultra-stable zeolite, ZSM- zeolite 5, zeolite ZSM-12, zeolite SSZ-3, zeolite SAPO 5, ofretite, bitumen zeolite, and mixtures thereof.
    [4]
    Treatment system according to any one of claims 1 to 3, characterized in that the inlet layer and / or the outlet layer additionally comprise a metal oxide support material, said support material being preferably selected of the group consisting of alumina, zirconia, zirconia-alumina, barium-alumina, lantana-alumina, lantana-zirconia-alumina, and mixtures thereof, wherein the metal oxide support material is preferably gamma-alumina which is
    Petition 870180166882, of 12/21/2018, p. 11/31
    2 preferably doped with a refractory metal and / or a rare earth metal, more preferably with lanthanum and / or zirconium.
    [5]
    Treatment system according to any one of claims 1 to 4, characterized in that the inlet layer and / or the outlet layer additionally comprise an oxygen storage component (OSC), said OSC preferably being selected from the group consisting of zirconia, ceria, barium, lantana, praseodymia, neodymia, and mixtures thereof, in which the CSO is more preferably ceria and / or zirconia, and even more preferably a ceria-zirconia composite.
    [6]
    Treatment system according to any one of claims 1 to 5, characterized in that the input layer and / or the output layer additionally comprise a NOx trapping component, said NOx trapping component preferably being selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, rare earth metal oxides, and mixtures thereof, wherein the NOx trapping component is more preferably barium oxide and / or strontium oxide, and even more preferably oxide barium.
    [7]
    Treatment system according to any one of claims 1 to 6, characterized in that the particulate filter substrate is a flow monolith, preferably a wall flow filter, the wall flow filter being preferably it has a honeycomb structure.
    [8]
    Treatment system according to any one of claims 1 to 7, characterized by the fact that the TWC catalyst is located upstream of the particulate filter.
    [9]
    Treatment system according to any one of claims 1 to 8, characterized in that the TWC catalyst comprises Rh and / or Pd, preferably Pd.
    Petition 870180166882, of 12/21/2018, p. 12/31
    [10]
    Treatment system according to any one of claims 1 to 9, characterized in that the TWC catalyst additionally comprises a metal oxide support material, said support material preferably being selected from the group consisting of alumina, zirconia, zirconia-alumina, barium-alumina, lanthanum-alumina, lanthanum-zirconia-alumina, and mixtures thereof, wherein the metal oxide support material is preferably gamma-alumina which is preferably doped with a refractory metal and / or a metal rare earth, more preferably with lanthanum and / or zirconium.
    [11]
    Treatment system according to any one of claims 1 to 10, characterized in that the TWC catalyst additionally comprises an OSC, said OSC preferably being selected from the group consisting of zirconia, ceria, barium, lantana, praseodymy, neodymia, and mixtures thereof, in which the CSO is more preferably ceria and / or zirconia, even more preferably ceria.
    [12]
    Treatment system according to any one of claims 1 to 11, characterized in that the NOx trap is located upstream of the particulate filter and preferably comprises a compound selected from the group consisting of alkali metal, metal oxides alkaline earth, and rare earth metal, and mixtures thereof, wherein more preferably the NOx trapper comprises barium oxide and / or strontium oxide, much more preferably barium oxide.
    [13]
    Treatment system according to claim 11, characterized in that the NOx trapper additionally comprises Pd, preferably Pd, Pt, and Rh.
    [14]
    Treatment system according to any one of claims 1 to 13, said system characterized by the fact that it additionally comprises:
    Petition 870180166882, of 12/21/2018, p. 13/31 a gasoline engine, where the gasoline engine is preferably a direct gasoline injection engine, and an exhaust gas duct in fluid communication with the engine, where the particulate filter substrate and the optional catalyst TWC and / or NOx trap are positioned inside the exhaust gas duct.
    [15]
    15. Method for the treatment of exhaust gas from a gasoline engine, characterized by the fact that it comprises:
    (i) providing a treatment system as defined in any of claims 1 to 14, and (ii) conducting a gasoline engine exhaust gas stream through the treatment system, wherein the exhaust gas stream preferably comprises hydrocarbons (HC), CO, NOx, and soot in a weight ratio of HC: CO: NO X : soot from (2.5 - 7.0): (0.5 - 3.0): (1.0 - 4.7): (0.00005 - 0.01).
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    同族专利:
    公开号 | 公开日
    WO2011015615A1|2011-02-10|
    CN102574056B|2014-09-17|
    EP2461895B1|2014-07-02|
    US20110030346A1|2011-02-10|
    ES2498727T5|2020-03-12|
    KR20120053506A|2012-05-25|
    KR101717802B1|2017-03-27|
    ES2498727T3|2014-09-25|
    CN102574056A|2012-07-11|
    PL2461895T5|2019-12-31|
    US8758695B2|2014-06-24|
    JP2013500857A|2013-01-10|
    BR112012002442A2|2016-03-01|
    JP5854995B2|2016-02-09|
    EP2461895A1|2012-06-13|
    PL2461895T3|2014-12-31|
    EP2461895B2|2019-07-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4329162A|1980-07-03|1982-05-11|Corning Glass Works|Diesel particulate trap|
    JP3347481B2|1994-07-15|2002-11-20|トヨタ自動車株式会社|Exhaust gas purification catalyst|
    US5830421A|1996-07-03|1998-11-03|Low Emissions Technologies Research And Development Partnership|Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process|
    WO2000029726A1|1998-11-13|2000-05-25|Engelhard Corporation|Catalyst and method for reducing exhaust gas emissions|
    US6375910B1†|1999-04-02|2002-04-23|Engelhard Corporation|Multi-zoned catalytic trap and methods of making and using the same|
    ES2284503T3|1999-07-02|2007-11-16|Basf Catalysts Llc|CATALYST SYSTEM TO TREAT EXHAUST GASES OF DIESEL ENGINES AND PROCEDURE.|
    US6492297B1|2000-09-15|2002-12-10|Engelhard Corporation|Catalyst composition for purifying exhaust gas|
    CA2423591A1|2000-09-29|2002-04-04|Omg Ag & Co. Kg|Catalytic soot filter and use thereof in treatment of lean exhaust gases|
    JP4439910B2|2001-08-01|2010-03-24|ジョンソン、マッセイ、パブリック、リミテッド、カンパニー|Gasoline engine with exhaust mechanism for burning particulate matter|
    US6421599B1|2001-08-09|2002-07-16|Ford Global Technologies, Inc.|Control strategy for an internal combustion engine in a hybrid vehicle|
    GB0125890D0|2001-10-27|2001-12-19|Johnson Matthey Plc|Exhaust system for an internal combustion engine|
    US7832203B2†|2001-10-27|2010-11-16|Johnson Matthey Public Limited Company|Exhaust system for a lean burn internal combustion engine|
    US6703343B2|2001-12-18|2004-03-09|Caterpillar Inc|Method of preparing doped oxide catalysts for lean NOx exhaust|
    US6915629B2|2002-03-07|2005-07-12|General Motors Corporation|After-treatment system and method for reducing emissions in diesel engine exhaust|
    JP2004016931A|2002-06-17|2004-01-22|Nissan Motor Co Ltd|Exhaust gas purification catalyst|
    US7229597B2|2003-08-05|2007-06-12|Basfd Catalysts Llc|Catalyzed SCR filter and emission treatment system|
    US7722829B2|2004-09-14|2010-05-25|Basf Catalysts Llc|Pressure-balanced, catalyzed soot filter|
    US7243488B2|2005-08-30|2007-07-17|Delphi Technologies, Inc.|Method and apparatus for controlling regeneration temperature in a diesel particulate trap|
    US7506504B2|2005-12-21|2009-03-24|Basf Catalysts Llc|DOC and particulate control system for diesel engines|
    JP5073303B2|2006-03-24|2012-11-14|日本碍子株式会社|Catalytic converter and manufacturing method of catalytic converter|
    US7550124B2|2006-08-21|2009-06-23|Basf Catalysts Llc|Layered catalyst composite|
    JP4787704B2|2006-09-15|2011-10-05|第一稀元素化学工業株式会社|Catalyst system used in automobile exhaust gas purification device, exhaust gas purification device using the same, and exhaust gas purification method|
    TWI449572B|2006-11-29|2014-08-21|Umicore Shokubai Japan Co Ltd|Oxidation catalyst and the oxidation catalyst using an exhaust gas purification system|
    US20080120970A1|2006-11-29|2008-05-29|Marcus Hilgendorff|NOx Storage Materials and Traps Resistant to Thermal Aging|
    CN101636564B†|2006-12-21|2012-07-04|约翰逊马西有限公司|Apparatus comprising lean burn ic engine and an exhaust system therefor|
    AT477849T|2007-03-19|2010-09-15|Umicore Ag & Co Kg|Palladium Rhodium Simple Layer Catalyzer|
    JP2009050789A|2007-08-27|2009-03-12|Tokyo Roki Co Ltd|Catalyst for cleaning exhaust gas|
    DE102007046158B4|2007-09-27|2014-02-13|Umicore Ag & Co. Kg|Use of a catalytically active particulate filter for the removal of particles from the exhaust gas of combustion engines operated with predominantly stoichiometric air / fuel mixture|
    AT457813T†|2007-09-28|2010-03-15|Umicore Ag & Co Kg|REMOVAL OF PARTICLES FROM THE EXHAUST GASES OF INTERNAL COMBUSTION ENGINES OPERATED BY STOCKWOMATIC AIR / FUEL MIXING|
    EP2318673B1†|2008-02-05|2019-09-18|BASF Corporation|Gasoline engine emissions treatment systems having particulate traps|
    GB0903262D0†|2009-02-26|2009-04-08|Johnson Matthey Plc|Filter|WO2008143792A1|2007-05-11|2008-11-27|Sdc Materials, Inc.|Formation of catalytic regions within porous structures using supercritical phase processing|
    US8507401B1|2007-10-15|2013-08-13|SDCmaterials, Inc.|Method and system for forming plug and play metal catalysts|
    EP2318673B1|2008-02-05|2019-09-18|BASF Corporation|Gasoline engine emissions treatment systems having particulate traps|
    US9090475B1|2009-12-15|2015-07-28|SDCmaterials, Inc.|In situ oxide removal, dispersal and drying for silicon SiO2|
    US8652992B2|2009-12-15|2014-02-18|SDCmaterials, Inc.|Pinning and affixing nano-active material|
    US9149797B2|2009-12-15|2015-10-06|SDCmaterials, Inc.|Catalyst production method and system|
    US20110143930A1|2009-12-15|2011-06-16|SDCmaterials, Inc.|Tunable size of nano-active material on nano-support|
    US9126191B2|2009-12-15|2015-09-08|SDCmaterials, Inc.|Advanced catalysts for automotive applications|
    EP2539040B1|2010-02-23|2018-07-18|Basf Se|Improved catalyzed soot filter|
    US8516804B2|2010-02-26|2013-08-27|Corning Incorporated|Systems and methods for determining a particulate load in a particulate filter|
    US8815189B2|2010-04-19|2014-08-26|Basf Corporation|Gasoline engine emissions treatment systems having particulate filters|
    EP2611535A4|2010-09-02|2014-05-21|Basf Se|Catalyst for gasoline lean burn engines with improved no oxidation activity|
    WO2012029051A1|2010-09-02|2012-03-08|Basf Se|Catalyst for gasoline lean burn engines with improved nh3-formation activity|
    US8669202B2|2011-02-23|2014-03-11|SDCmaterials, Inc.|Wet chemical and plasma methods of forming stable PtPd catalysts|
    JP2012219732A|2011-04-11|2012-11-12|Toyota Motor Corp|Pm filter and method of regenerating the same|
    EP2707118B1|2011-05-13|2019-12-04|Basf Se|Catalyzed soot filter with layered design|
    DE102011050788A1|2011-06-01|2012-12-06|Ford Global Technologies, Llc.|Exhaust gas aftertreatment device and method for a gasoline engine|
    CN103945919A|2011-08-19|2014-07-23|Sdc材料公司|Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions|
    JP5720949B2|2011-12-08|2015-05-20|トヨタ自動車株式会社|Exhaust gas purification catalyst|
    US9239019B2|2012-01-26|2016-01-19|Ford Global Technologies, Llc|Particulate matter retaining system|
    EP2650042B2|2012-04-13|2020-09-02|Umicore AG & Co. KG|Pollutant abatement system for gasoline vehicles|
    GB201207313D0|2012-04-24|2012-06-13|Johnson Matthey Plc|Filter substrate comprising three-way catalyst|
    EP2858738B1|2012-06-06|2019-11-20|Umicore Ag & Co. Kg|Three-way-catalyst system|
    JP6386449B2|2012-06-06|2018-09-05|ユミコア アクチェンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト|Start-up catalyst for use upstream of a gasoline particulate filter|
    JP5939140B2|2012-11-20|2016-06-22|マツダ株式会社|Particulate filter with catalyst|
    US9156025B2|2012-11-21|2015-10-13|SDCmaterials, Inc.|Three-way catalytic converter using nanoparticles|
    US9511352B2|2012-11-21|2016-12-06|SDCmaterials, Inc.|Three-way catalytic converter using nanoparticles|
    KR101427933B1|2012-12-28|2014-08-11|현대자동차 주식회사|Catalytic converter of internal combustion engine and apparatus of purifying exhaust gas provided with the same|
    GB201302686D0|2013-02-15|2013-04-03|Johnson Matthey Plc|Filter comprising three-way catalyst|
    US20160001229A1|2013-03-07|2016-01-07|Cummins Ip, Inc.|Particulate matter filter with catalytic elements|
    JPWO2014148584A1|2013-03-22|2017-02-16|日本碍子株式会社|Heat exchanger|
    GB2512648B|2013-04-05|2018-06-20|Johnson Matthey Plc|Filter substrate comprising three-way catalyst|
    GB2513364B|2013-04-24|2019-06-19|Johnson Matthey Plc|Positive ignition engine and exhaust system comprising catalysed zone-coated filter substrate|
    WO2014178632A1|2013-05-02|2014-11-06|희성촉매 주식회사|Catalyst system for purifying exhaust gas from gasoline engine|
    WO2014178633A1|2013-05-02|2014-11-06|희성촉매 주식회사|Gasoline particulate filter for gasoline direct injection engine|
    GB2517035C|2013-05-31|2020-02-26|Johnson Matthey Plc|Catalyzed filter for treating exhaust gas|
    RU2660737C2|2013-05-31|2018-07-09|Джонсон Мэтти Паблик Лимитед Компани|Catalysed filter for treating exhaust gas|
    DE102013210270A1|2013-06-03|2014-12-04|Umicore Ag & Co. Kg|three-way|
    EP3024571B1|2013-07-25|2020-05-27|Umicore AG & Co. KG|Washcoats and coated substrates for catalytic converters|
    JP2015047517A|2013-08-29|2015-03-16|マツダ株式会社|Catalyst for exhaust gas purification and production method thereof|
    MX2016004759A|2013-10-22|2016-07-26|Sdcmaterials Inc|Compositions of lean nox trap.|
    KR20160074566A|2013-10-22|2016-06-28|에스디씨머티리얼스, 인코포레이티드|Catalyst design for heavy-duty diesel combustion engines|
    US10335736B2|2013-12-11|2019-07-02|Cataler Corporation|Exhaust gas purification material|
    WO2015087816A1|2013-12-11|2015-06-18|株式会社キャタラー|Exhaust gas purification material|
    US9463447B2|2014-01-29|2016-10-11|Ford Global Technologies, Llc|Hydrocarbon trap with increased zeolite loading and improved adsorption capacity|
    US9744529B2|2014-03-21|2017-08-29|Basf Corporation|Integrated LNT-TWC catalyst|
    EP3119500A4|2014-03-21|2017-12-13|SDC Materials, Inc.|Compositions for passive nox adsorptionsystems|
    JP6564637B2|2014-10-09|2019-08-21|株式会社キャタラー|Exhaust gas purification device|
    WO2016056573A1|2014-10-09|2016-04-14|株式会社キャタラー|Exhaust gas purification device|
    JP6381663B2|2014-10-16|2018-08-29|株式会社キャタラー|Exhaust gas purification catalyst|
    EP3207990B1|2014-10-16|2021-04-28|Cataler Corporation|Exhaust gas purification catalyst|
    US10344655B2|2014-10-16|2019-07-09|Cataler Corporation|Exhaust gas purification catalyst|
    JP6293638B2|2014-10-17|2018-03-14|株式会社キャタラー|Exhaust gas purification device|
    JP6279448B2|2014-10-17|2018-02-14|株式会社キャタラー|Exhaust gas purification device|
    US9650930B2|2015-01-12|2017-05-16|Ford Global Technologies, Llc|Emission control device regeneration|
    EP3268115A4|2015-02-11|2019-03-06|SDCmaterials, Inc.|Lean nox traps, trapping materials, washcoats, and methods of making and using the same|
    WO2016130926A2|2015-02-13|2016-08-18|SDCmaterials, Inc.|Zoned catalytic converters for gasoline engines with reduced rhodium content|
    EP3254759B1|2015-02-17|2019-04-03|Cataler Corporation|Exhaust gas purification catalyst|
    JP6472677B2|2015-02-17|2019-02-20|株式会社キャタラー|Exhaust gas purification catalyst|
    US10159934B2|2015-02-17|2018-12-25|Cataler Corporation|Exhaust gas purification catalyst|
    CN111271157A|2015-07-09|2020-06-12|优美科股份公司及两合公司|System for removing particulate matter and harmful compounds from engine exhaust|
    US9987626B2|2015-08-20|2018-06-05|Ford Global Technologies, Llc|Use of transition metals to reduce cold start emissions|
    CN108138617B|2015-09-24|2020-11-06|本田技研工业株式会社|Exhaust gas purifying filter|
    CN108138618B|2015-09-24|2020-06-16|本田技研工业株式会社|Exhaust gas purification system for internal combustion engine|
    GB2546164A|2015-09-30|2017-07-12|Johnson Matthey Plc|Gasoline particulate filter|
    GB2543337A|2015-10-15|2017-04-19|Johnson Matthey Plc|Exhaust System|
    KR101745169B1|2015-11-04|2017-06-08|현대자동차주식회사|Muffler integrated type gasoline particulate filter|
    US9764287B2|2015-11-06|2017-09-19|Paccar Inc|Binary catalyst based selective catalytic reduction filter|
    US10058819B2|2015-11-06|2018-08-28|Paccar Inc|Thermally integrated compact aftertreatment system|
    JP6738185B2|2016-04-07|2020-08-12|株式会社キャタラー|Exhaust gas purification device|
    JP6372513B2|2016-04-13|2018-08-15|トヨタ自動車株式会社|Catalytic converter|
    EP3476480A4|2016-06-23|2020-03-04|N.E. Chemcat Corporation|Catalyst for lean burn|
    CN109477408A|2016-08-05|2019-03-15|巴斯夫公司|Quadruple effect reforming catalyst for petrol engine emission treatment systems|
    WO2018024546A1|2016-08-05|2018-02-08|Basf Se|Monometallic rhodium-containing four-way conversion catalysts for gasoline engine emissions treatment systems|
    US20190193067A1|2016-08-26|2019-06-27|N.E. Chemcat Corporation|Honeycomb structure, honeycomb structure type catalyst and production methods therefor|
    JP6346642B2|2016-09-26|2018-06-20|株式会社キャタラー|Exhaust gas purification catalyst|
    CN110382830A|2017-03-23|2019-10-25|优美科股份公司及两合公司|Catalytic activity particulate filter|
    US10675586B2|2017-06-02|2020-06-09|Paccar Inc|Hybrid binary catalysts, methods and uses thereof|
    US10835866B2|2017-06-02|2020-11-17|Paccar Inc|4-way hybrid binary catalysts, methods and uses thereof|
    IT201700101864A1|2017-09-12|2019-03-12|Fca Italy Spa|PARTICULATE FILTER FOR A GASOLINE INTERNAL COMBUSTION ENGINE|
    EP3501646A1|2017-12-19|2019-06-26|Umicore Ag & Co. Kg|Catalytically active particle filter|
    EP3505246B1|2017-12-19|2019-10-23|Umicore Ag & Co. Kg|Catalytically active particle filter|
    CN108979798B|2018-03-28|2021-03-23|昆明贵研催化剂有限责任公司|Gasoline vehicle particle trapping catalyst and preparation method thereof|
    CN111867723B|2018-03-29|2021-11-23|三井金属矿业株式会社|Exhaust gas purifying composition, exhaust gas purifying catalyst comprising same, and exhaust gas purifying catalyst structure|
    JPWO2020039649A1|2018-08-22|2021-09-30|三井金属鉱業株式会社|Exhaust gas purification catalyst|
    FR3088369A1|2018-11-08|2020-05-15|Psa Automobiles Sa|VEHICLE HAVING A CONTROLLED IGNITION ENGINE AND A SELF-REGENERATING PARTICLE FILTER AND ASSOCIATED CONTROL METHOD|
    FR3088368A1|2018-11-08|2020-05-15|Psa Automobiles Sa|VEHICLE EQUIPPED WITH A SELF-REGENERATING PARTICLE FILTER AND A MOTOR AND METHOD FOR CONTROLLING THE SAME|
    US11253840B2|2018-12-13|2022-02-22|Johnson Matthey Public Limited Company|Transition metal doped alumina for improved TWC performance|
    GB2583581A|2019-03-29|2020-11-04|Johnson Matthey Plc|A catalyst article and the use thereof for filtering fine particles|
    US11007514B2|2019-04-05|2021-05-18|Paccar Inc|Ammonia facilitated cation loading of zeolite catalysts|
    US10906031B2|2019-04-05|2021-02-02|Paccar Inc|Intra-crystalline binary catalysts and uses thereof|
    WO2020219376A1|2019-04-22|2020-10-29|Basf Corporation|Catalyzed gasoline particulate filter|
    US10934918B1|2019-10-14|2021-03-02|Paccar Inc|Combined urea hydrolysis and selective catalytic reduction for emissions control|
    WO2021145326A1|2020-01-14|2021-07-22|三井金属鉱業株式会社|Exhaust gas purification system|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-11-06| B06T| Formal requirements before examination|Free format text: O DEPOSITANTE DEVE RESPONDER A EXIGENCIA FORMULADA NESTE PARECER POR MEIO DO SERVICO DE CODIGO 206 EM ATE 60 (SESSENTA) DIAS, A PARTIR DA DATA DE PUBLICACAO NA RPI, SOB PENA DO ARQUIVAMENTO DO PEDIDO, DE ACORDO COM O ART. 34 DA LPI.PUBLIQUE-SE A EXIGENCIA (6.20). |
    2019-04-24| B09A| Decision: intention to grant|
    2019-05-28| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/08/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/08/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    US23146109P| true| 2009-08-05|2009-08-05|
    US61/231461|2009-08-05|
    EP09167270|2009-08-05|
    EP09167270.9|2009-08-05|
    PCT/EP2010/061390|WO2011015615A1|2009-08-05|2010-08-05|Treatment system for gasoline engine exhaust gas|
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