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    • 专利摘要:
    THREE-WAY CATALYTIC SYSTEM THAT HAS A MULTI-LAYER CATALYST IN THE AMOUNT The present invention relates to a stratified, three-way catalyst for conversion that has the ability to simultaneously catalyze the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides, being separated into an anterior and posterior portion. A catalytic material with at least two front and two back layers is provided together with a substrate, where each layer includes a support, all layers comprise a metal component of the platinum group and the bottom back layer is substantially free of an oxygen storage component (OSC) that contains cerium oxide.
    公开号:BR112013011920B1
    申请号:R112013011920-9
    申请日:2011-11-21
    公开日:2020-06-30
    发明作者:John G. Nunan；Raoul Klingmann；Ryan J. Andersen；Davion Onuga Clark；David Henry Moser
    申请人:Umicore Ag & Co. Kg；
    IPC主号:
    专利说明:

    [0001] The invention relates generally to overlapping catalysts used to treat gaseous streams that contain hydrocarbons, carbon monoxide and nitrogen oxides. More specifically, this invention is directed to catalysts for three-way conversion (TWC) that have more than one catalyst layer upstream and a multilayer catalyst that is located downstream. BACKGROUND AND PREVIOUS TECHNIQUE
    [0002] Current TWC catalysts are used to control the mobile emission of Otto engines. The technology is well developed with emission reduction capabilities of> 99% for CO, HC (hydrocarbons) and NOx (nitrogen oxides) after heating to operating temperatures greater than 250 ° C. Typical TWC catalyst configurations consist of a single brick or multiple bricks system in the vehicle's exhaust line. If more than one catalyst is used, the catalysts can be located in a single converter, adjacent or separated by a space defined as in separate converters. A common design for large engines is to have one converter in a closed coupling (DC) position (near the collector) with the second converter in the bottom of the body (UB) cooler. As approximately all mobile emission control systems are passive in nature, the time to heat the catalyst to the operating temperature is critical, as described in EP1900416, which is invoked and incorporated here by the reference in its entirety.
    [0003] Therefore, CC catalyst designs consist of features that favor rapid heating such as light, small size substrates (small thermal inertia), high cell density (improved mass & heat transfer) and high platinum group metal loading ( PGM (eg platinum, palladium, rhodium, rhenium, ruthenium and iridium). On the other hand, the UB catalyst can have a higher volume and a lower cell density (lower pressure drop) and more often contain a lower PGM load. For smaller vehicles that operate at high RPM, only one converter is typically used, usually located in the CC position. A disadvantage of locating catalysts near the collector is increased thermal degradation and faster loss of activity, especially under conditions of high / high speed loading that result in loss of supporting surface area or pore volume and rapid sintering of the PGN .
    [0004] Modern TWC catalysts use a variety of strategies to limit or delay thermal degradation, such as stable large surface area alumina supports for PGMs, the addition of promoters and stabilizers and advanced oxygen storage components (CSOs) that enhance performance and degrade at a lower rate (see, for example, US5672557, which is considered and incorporated into this by reference in its entirety).
    [0005] In technique, certain design strategies have been used to balance performance with associated costs. These strategies include selecting the type and distribution of PGM, substrate volume, cell density, WC overlap and composition of the various WC layers.
    [0006] An important design feature for TWC technologies is the proper separation and configuration of both PGM and washcoat (WC) components in separate WC layers and / or in separate bricks , if multiple bricks systems are used. The most modern TWC catalysts can have one or more WC layers, the most common being 2-layer systems. See, for example, EP1541220, US 5981427, WO09012348, W008097702, W09535152, US7022646, US5593647, which are considered and incorporated herein by reference in their entirety.
    [0007] For PGMs, the most common approach is to locate the nent made up Rh and optionally Pt on the top or 2 to WC layer with Pd preferably located at the bottom or 1 to WC layer (see, for exam-ple, US5593647). The separation of both toilet components and PGMs can also be achieved by unique bricks by zoning, through which the front or rear zone or section of a toilet layer can consist of different support components or different or more commonly PGM components , different concentrations of a given PGM such as Pd. An advantage to separating PGMs into layers or zones is that more optimum supports and promoters for each PGM can be used in order to maximize overall performance.
    [0008] Prior to the present invention, researchers were attracted to certain different toilet composition configurations that are considered to represent the preferred configuration for the best performance. Thus, UB for two layers of catalysts, Rh is invariably located in the upper layer (2a) with Pt optionally present, while Pd is located in the first or lower layer (see, for XAMPLE e, US5593647). In addition, both the upper (2 a ) and lower (1 a ) layers ideally contain a large surface area refractory oxide support such as gamma or gamma / theta / delta alumina with the further addition of promoters, stabilizers and a component adequate oxygen storage (OSC). This WC project is described in detail in Sung et al. (US6087298) and Hu et al. (US6497851) included here for reference purposes. Both, Sung et al. and Hu et al., also described preferred WC compositions and configurations for the CC catalysts or zones at the inlets for the exhaust gas flow. Therefore, for the CC entrance or entrance zone (anterior), the WC design is preferably free of an OSC and consists of a large surface area refractory oxide support such as gamma or gamma / theta / delta alumina with stabilizers and appropriate additives. On the other hand, it is preferable that the posterior catalyst, zone or UB catalyst, have an OSC present in the lower and upper layers. These and other aspects are described, for example, in Hu et al. and in the references cited here.
    [0009] Within the TWC catalyst field, new technologies and toilet configurations and systems are needed to meet increasingly stringent emission standards and the need to delay catalyst deactivation and achieve increasingly increasing performance at low PGM loads. SUMMARY OF THE INVENTION
    [0010] This invention relates to TWC catalysts that have different compositions with respect to their locations in relation to each other and their use in emission control systems. Specifically, the TWC catalysts according to the present invention comprise at least one brick or front zone (upstream) and one brick or back zone (downstream). Both, the anterior or posterior bricks or zones comprise at least two layers; however, in brick or rear area, an OSC is absent in the first catalyst layer (bottom). In some modalities, one or more bricks or zones can be placed between the anterior and posterior bricks or zones. In some modalities, the zones or bricks are located in a single converter, adjacent or separated by a defined space. In some modalities, the bricks are located in separate converters. In some embodiments, there are provided two or more separate converters and a converter contains at least one further zone or brick with at least two layers and absence of CSO in the first catalytic layer. In some embodiments comprising more than one separate converter, the converter further downstream zone contains a brick or higher with at least two layers and absence of CSO in the first catalytic layer.
    [0011] In some embodiments, the invention is directed to a catalytic composite for the purification of exhaust gases from a combustion engine, which occurs substantially under stoichiometric conditions, which comprises in sequence and in order: a previous dual layer configuration on a substrate having a first previous catalytic layer (bottom) and a catalytic layer 2 to the previous (higher); and a backsheet double configuration on a substrate having a first subsequent catalytic layer (bottom) and a subsequent catalytic layer 2 (top); wherein the above catalytic layer 2 and the second catalytic layer further comprises a metal compound of the platinum group (PGM) such as palladium; and 1 wherein the subsequent catalytic layer is substantially free of an oxygen storage component (OSC).
    [0012] In some embodiments of the present invention, the above catalytic layer 2 and the second catalytic layer subsequent to form a continuous layer. In some embodiments, the continuous layer may have a gradient from the upstream end to the downstream end. In some embodiments, the two previous catalytic layer 2 and the rear catalytic layer are made of the same materials in the same or different concentrations.
    [0013] With reference to the first and the second layers, no limitation being placed on the location of the layer in view of the direction of the x flu- exhaust. The locations of the layers in view of the exhaust flow are more described as anterior (upstream) and posterior (downstream) layers. A first layer of the catalytic material is deposited on a substrate or on a lower layer already deposited on the substrate to form a lower cladding. A second catalytic layer is deposited over and in physical contact with the first layer to form the topcoat.
    [0014] In other words, the previous zone or brick (upstream) that comes into contact with the first exhaust is closer to the engine and may have a lower catalytic layer (1 a ) and an upper catalytic layer (2 a ). The posterior zone or brick (downstream) is that which comes into contact with exhaustion after contact with the previous zone or brick . The posterior zone or brick may have a lower catalytic layer (1 a ) and an upper catalytic layer (2 a ). The front and rear zones or bricks can be in the same converter and can be touching each other or separated by a distance, for example, about 2.5 cm (1 inch) or more. Alternatively, the anterior and posterior zones or bricks can be in separate converters, which can be separated by a greater distance, for example, about 30 to 180 cm (1 to 6 feet).
    [0015] The term "substantially free of an oxygen storage component (OSC)" refers to having a very small amount or, preferably, no OSC in, for example, a given layer. A very small amount of OSC is understood to mean less than or equal to about 1%, preferably about 0.5%, more preferably about 0.25% and most preferably about 0.1% by weight of OSC in a given layer.
    [0016] In some embodiments, an exhaust treatment system is provided that comprises the catalyst composite. The exhaust treatment system can also comprise one or more exhaust treatment devices selected from the group consisting of filters to capture particulate matter from gasoline (GTP), capture HC and NOx-absorbing catalysts.
    [0017] In some embodiments, the present invention provides methods for treating exhaust gases which comprise contacting a gas stream comprising hydrocarbons, carbon monoxide and nitrogen oxides with a layered catalyst composite or an exhaust treatment system as described herein, wherein the catalytic material employed is effective in substantially simultaneously oxidizing carbon monoxide and hydrocarbons and reducing nitrogen oxides. In some embodiments, the temperature of the exhaust gas at the inlet of the catalyst can vary from room temperature to as high as 1100 ° C, however, the typical operating temperatures of the catalyst by the project are within the range of about 300 to 900 ° C .
    [0018] The foregoing general description and the following detailed description are for example and explanation only and are intended to provide a further explanation of the invention as claimed. The accompanying drawings are included to provide a further understanding of the invention and are incorporated and form part of that application, illustrate various modalities of the invention, and together with a description serve to explain the principles of the invention. BRIEF DESCRIPTION OF THE FIGURES
    [0019] The present invention will be understood with reference to the figures, in which: Figures 1a to 1e are examples of stratification and known washcoat configurations . Figures 2 a and 2b are examples of stratification and washcoat configurations of the present invention, where the first layer of the zone (Fig. 2a) or brick (Fig. 2b) posterior does not have OSC. Fig. 3 illustrates another embodiment of the present invention. Fig. 4a shows a WC configuration for a reference catalyst (prior art) that uses a conventional 2-layer design comprising uniform layers of Rh and Pd. FIG. 4b shows a toilet configuration for a catalyst according to the present invention, wherein the first catalytic zone or layer of INFE-rior / rear brick is no OSC. Fig. 5 is an FTP evaluation graph of the inventive system configuration described in Figure 4a / b after 50 hours of thermal aging in 4 modes; Vehicle = 2005 MY, BIN 5, 2.2L / 4 cylinders with sequential fuel injection. Pd + Rh = 20 g / ft 3 @ 0: 9: 1; Average of three FTP tests for each catalyst system, comparing a reference sample 4a and a test sample 4B for THC performance. Fig. 6 is a graph of the FTP evaluation of the inventive system configuration described in Figure 4a / 4b after 50 hours of thermal aging in 4 modes; Vehicle = 2005 MY, BIN 5, 2.2L / 4 cylinders with sequential fuel injection. Pd + Rh = 20 g / ft 3 @ 0: 9: 1; Average of three FTP tests for each catalyst system, comparing a reference sample 4a and a test sample 4B for NOx performance. DETAILED DESCRIPTION OF THE INVENTION
    [0020] The present invention is directed to a catalyst for three-way conversion (TWC) and the compositions and locations of the catalytic layers in relation to the direction of the exhaust gas flow. In particular, the TWC catalysts according to the present invention comprise at least one brick or back zone (upstream) and one brick or back zone (downstream), wherein the brick or back zone comprises at least 2 layers wherein an OSC is absent in the first catalyst layer (bottom). As described herein, the TWC catalysts according to the present invention provide great performance benefits that are unexpected based on the teachings and best practices in the prior art for the present invention.
    [0021] The present invention relates to a stratified catalytic composite of the type generally referred to as a three-way conversion catalyst (TWC) which has the ability to simultaneously catalyze the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides. The catalyst composite is divided into at least two sections by using different zones on a substrate or by using separate bricks that are located in a single converter, adjacent, or separated by a space defined as in separate converters.
    [0022] In some embodiments, the loading of the platinum group metal (PGM) of the catalytic layers is about 0.001 to 20% by weight. In some embodiments, each layer of the catalytic layers may comprise a different composition. In some embodiments, each bed has a load between about 0.2 to 2.8 g / inch 3 . In some embodiments, each layer has a PGM loading between about 0.01% by weight to 20% by weight of the layer. In some embodiments, each of the respective layers is deposited in a PGM load of about 0.02 to 15.0% by weight.
    [0023] In some embodiments, the catalyst composite refers to a PGM content of the layers which is as follows: 1 the previous catalytic layer - 0.1 to about 12.0% by weight of the layer; 1 the posterior catalytic layer - 0.05 to about 6.0% by weight of the layer; 2 the previous catalytic layer - 0.01 to about 12.0% by weight of the layer; 2 the posterior catalytic layer - 0.01 to about 6.0% by weight of the layer. The subsequent second catalytic layer always comprising rhodium as PGM, but can also comprise other PGMs. Rh is preferred in the subsequent catalytic layer 2 since the reduction of NOx, based on the reaction 2NO + 2CO → N 2 + 2CO 2 is more efficient at intermediate temperatures in the range of 300 to 600 ° C. In some embodiments, the amount of rhodium in one layer is about 0.01 to 1.0% by weight, preferably 0.02 to 0.5% and most preferably 0.05 to 0.25% by weight. The anterior and posterior 1 st catalytic layers always comprise palladium as a PGM, but also comprise other PGMs. In a preferred embodiment, the first anterior and posterior layers comprise only catalytic palladium as PGM. Palladium is particularly effective for the oxidation of HC and is generally concentrated in the first catalytic layer prior to the previous brick in order to start the HC light-off operation as quickly as possible. This increases since the concentration of HC emitted by the engine is higher in the initial stages of operation of the vehicle in contrast to NOx, which is emitted widely after heating the vehicle. In some embodiments, the amount of palladium in the anterior and posterior catalytic layers is about 0.1 to 15.0% by weight, preferably about 0.2 to 10.0% and most preferably about 0, 5 to 5.0% by weight.
    [0024] As already indicated, it may be advantageous to have Pt as a PGM present in the layers, especially in the anterior and posterior 2 to catalytic layers. Pt has the advantage of being particularly effective for oxidizing hard HCs (saturated HCs) and can advantageously form alloys with Rh. Under normal stoichiometric / rich / poor exhaust gas conditions, the alloy surface is rich in Rh which protects this PGM from negative interactions with the support.
    [0025] In some embodiments, an amount of metal in the platinum group is up to about 4% by weight of the layer. In some embodiments, the amount of platinum in a layer is about 0.05 to 5% by weight, preferably about 0.1 to 2.0% by weight and most preferably about 0.3 to 1, 0% by weight. In some embodiments, the platinum content of the layers is as follows: 2 the previous catalytic layer - about 0.05 - 5.0% by weight of the layer, preferably about 0.1 - 2.0%, and most preferably about 0.3 - 1.0%; 2 the posterior catalytic layer - 0.025 - 2.5% by weight of the layer, preferably about 0.1 - 2.5%, and most preferably about 0.3-1.0%.
    [0026] The reference to OSC (oxygen storage component) refers to an entity that has a multi-valence state and can react actively with oxidants such as oxygen or nitrogen oxides under oxidative conditions or reacts with reducers such as carbon monoxide ( CO), hydrocarbons (HCs) or hydrogen under reduced conditions. Suitable oxygen storage components may include one or more oxides of rare-earth or transition metals selected from the group consisting of cerium, zirconium, terbium, iron, copper, manganese, cobalt, praseodymium, lanthanum, yttrium, samarium, gadolinium , dysprosium, iterbium, niobium, neodymium, and mixtures of two or more of these. Examples of suitable oxygen storage components include cerium oxide, praseodymium oxide or combinations thereof.
    [0027] The release of an OSC to the layer can be achieved by using, for example, mixed oxides. For example, cerium oxide can be released by a mixed cerium and zirconium oxide and / or a mixed cerium, zirconium and neodymium oxide with optionally other rare earths such as lanthanum or yttrium also present. For example, praseodymium oxide can be released by a mixed praseodymium and zirconium oxide and / or a mixed praseodymium, cerium, lanthanum, yttrium, zirconium and neodymium oxide. Suitable compositions can be found in US6387338 and US6585944, both of which are incorporated by reference in their entirety.
    [0028] OSC can be present up to about 80% by weight of the layer, about 20 to 70% and most preferably about 30 to 60%. The content of cerium oxide or praseodymium oxide is in the range of about 3 to 98%, preferably about 10 to 60%, most preferably about 20 to 40% by weight of the OSC. Suitable oxygen storage components may include one or more oxides of one or more rare-earth or transition metals selected from the group consisting of cerium, zirconium, terbium, iron, copper, manganese, cobalt, praseodymium, lanthanum, yttrium, samarium, gadolinium, dysprosium, ytterbium, niobium, neodymium, and mixtures of two or more of these. In some embodiments, the catalytic composite according to the invention comprises an oxygen storage component (OSC) content by weight of the layer as follows: 1 the previous catalytic layer - about 10 - 80% by weight of the layer, preferably about 20 - 70%, and most preferably about 30 - 60%; 2 the previous catalytic layer - about 10 - 80% by weight of the layer, preferably about 20 - 70%, and most preferably about 30 - 60%; 2 the posterior catalytic layer - about 10 - 80% by weight of the layer, preferably about 20 - 70%, and most preferably 20 about 30 - 60%.
    [0029] In some embodiments, the catalyst composite additionally comprises exhaust treatment materials selected from the group consisting of hydrocarbon storage components, NOx storage components since the current design may have particular applicability for exhaust treatment systems that comprise HC captors and / or NOx absorption functionality. Current technique catalyzed HC captors designs use an inner layer (UC - see later) that consists of materials that capture HC including several zeolites with an upper layer (OC) of One- or two-layer TWC, described in Japanese patents JP7124468 and JP7124467 and US 7442346, which are incorporated herein by reference. Optimum performance is obtained projects through which the first layer contains no OSC and where two subsequent catalytic layer contains an OSC as described herein for the optimum configuration of WC composition on 1 st and 2 nd catalytic layers prior and later technology. Additionally, the newest design for the HC capture location is in the rear cooler or in the lower body (UB) location (US7442346), unlike previous strategies for placing the HC capture in the CC position (US 5772972 ; Silver R. G, Dou D., Kirby CW, Richmond RP, Balland J „and Dunne S .; SAE 972843, and references therein) again in line with the current configuration of toilet layers. For the NOx absorber catalysts, a preferred location of the absorber is again at the location of the UB cooler with an active TWC also present to generate H 2 and for complete combustion of HC / CO during the rich / poor transitions.
    [0030] A suitable support according to some embodiments of the present invention is a refractory oxide support. The reference to a support "in a catalyst layer refers to a material on or within which platinum group metals, stabilizers, promoters, binders or other additives and the like are dispersed or impregnated, respectively. A support can be activated and / or stabilized as desired Examples of supports include, but are not limited to, large surface area refractory metal oxides, composites containing oxygen storage components and molecular sieves as is well known in the art. each layer independently comprises a compound that is activated, stabilized or both, selected from the group consisting of, but not limited to, alumina, silica, silica-alumina, alumina silicates, alumina-zirconia, lanthanum-alumina, lanthanum- zirconia-alumina, barium-alumina, barium-lanthanum-alumina, alumina-chromium and alumina-cerium.The support can comprise any suitable material, for example, a metal oxide such that it comprises gamma-alumina or a stabilized gamma-alumina promoter which has a specific surface area of about 50 to 350 m 2 / g, preferably about 75 to 250 m 2 / g and more preferably about 100 to 200 m 2 / g. In some modalities, the alumina present in any of the layers optionally comprises zirconia- and lanthanum- gamma-alumina stabilized in a loading of about 5 to 90% by weight of the layer, preferably about 20 to 70% and most preferably about 30 to 60%. For example, a suitable stabilized alumina may comprise about 0.1 to 15% by weight of lanthanum oxide (preferably as a stabilizer), preferably about 0.5 to 10% and most preferably about 1 to 7 %; and / or about 0.5 to 15%; preferably about 0.5 to 10% and most preferably about 1 to 7% zirconia (preferably as a gamma-alumina stabilizer). In some embodiments, alumina comprises barium oxide-stabilized gamma-alumina, neodymium oxide, lanthanum oxide and combinations thereof. The stabilizer loading onto a suitable alumina is about 0 to 4% by weight of the support, preferably about 1 to 3% and most preferably about 2% barium oxide. It is observed that lanthanum, zirconia and neodymium or a combination of these can be present in 0.1 to 15% by weight.
    [0031] In some embodiments, a molecular sieve material can be selected from the group consisting of faujasite, chabazite, silicalite, zeolite X, zeolite Y, ultra-stable zeolite Y, ofretite, Beta, ferrierite and ZSM / MFI zeolites. In particular, ion-exchanged Beta zeolites can be used, such as Fe / Beta zeolite or preferably H / Beta zeolite. Zeolites, preferably Beta zeolites, can have a molar ratio of silica to alumina. Zeolites, preferably Beta zeolites can have a silica / alumina molar ratio of at least about 25/1, or at least about 50/1, with useful ranges between about 25/1 to 1000/1, 50 / 1 to 500/1 as well as about 25/1 to 300/1, for example.
    [0032] In some embodiments, the layers are provided one above the catalytic layer and / or the subsequent first catalytic layer comprising stabilized alumina such as gamma alumina, which may be present in an amount 30 in about the range of 1- 90% by weight of the layer, preferably about 20 to 70% and most preferably about 60%, substantially only palladium, which can be present in an amount in the range of about 0.1 to 10% by weight of the layer , preferably about 0.1 to 5.0% and most preferably about 0.2 to 2.0%.
    [0033] In some embodiments, the two previous catalytic layers and further comprising stabilized alumina such as gamma alumina, which may be present in an amount in the range of about 10 to 90% by weight of the layer, preferably about 20 to 70% and most preferably about 30 to 60%; rhodium, which can be present in an amount in the range of about 0.1 to 1.0% by weight of the layer, preferably about 0.05 to 0.5% and most preferably about 0.1 to 0.25%.
    [0034] In some embodiments, the two previous catalytic layers and further comprises a stabilized alumina, such as stabilized gamma alumina with lanthanum oxide, which may be present in an amount in the range of about 10 to 90% by weight of the layer, preferably about 20 to 70% and most preferably about 30 to 60%; platinum, which can be present in an amount in the range of about 4% by weight of the layer, preferably about 0.05 to 2% and most preferably about 0.1 to 1.0%, according to what rhodium can be present in an amount in the range of about 0.01 to about 1.0% by weight of the layer, preferably about 0.05 to 0.5% and most preferably about 0.1 to 0 , 25%.
    [0035] In some embodiments, it may be desirable that a given layer further comprises up to about 40%, preferably about 5 to 30% and most preferably about 10 to 20% of a stabilizer comprising one or more non-metal oxides reducible, in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium and their mixtures. A layer can further comprise, according to one embodiment, 0 to about 40%, preferably about 5 to 30% and most preferably about 10 to 30% of one or more promoters comprising one or more earth metals -rays or transitions selected from the group consisting of lanthanum, praseodymium, yttrium, zirconium, samarium, gadolinium, dysprosium, ytterbium, niobium, neodymium and their mixtures. A layer can further comprise, according to one embodiment, 0 to about 20%, preferably about 2 to 20% and most preferably about 5 to 10% of one or more binders comprising one or more bohemite alumina, hydroxides zirconia or silica solutions and mixtures thereof. A layer can further comprise, according to an embodiment, 0 to about 20%, preferably about 0 to 12% and most preferably about 0 to 6% of one or more additives comprising hydrogen sulfide (H 2 S ), control agents such as nickel, iron, zinc, boron, manganese, strontium and mixtures thereof.
    [0036] Segregated washcoats that carry certain catalytic functionality can be used. The use of at least two layers on a substrate can lead to more efficient use and / or a decrease in the overall amount, for example, of metals in the platinum group due to their separation from each other.
    [0037] In some embodiments, the compositions of each layer are designed to convey a particular function of the TWC catalyst. For example, topcoat layers that are substantially free of platinum group metals and that comprise alumina and one or more base metal oxides are, for example, effective for trapping venoms such as sulfur, nitrogen, magnesium, calcium, zinc and phosphorus. Examples of base metal oxides include, but are not limited to, SrO, La 2 O 3 , Nd 2 O 3 , or BaO.
    [0038] The catalyst composite in its zoned form comprises a substrate comprising an axial inlet end, an axial outlet end, wall elements having a length that extends between the axial inlet end to the axial outlet end and a plurality of axially closed channels defined by the elements of the wall; and a front part of the catalyst composite deposited on the wall elements adjacent the axial inlet end having a length that extends less than the length of the wall of the wall elements, wherein the inlet catalyst composite comprises the catalyst composite described above. This catalyst composite further comprises a rear portion of the catalyst composite adjacent to the axial outlet end and having a length that extends for less than the length of the wall elements. For example, the front part of the catalyst composite may comprise (a) a substrate; (b) the first catalytic layer deposited onto the substrate, the first catalytic layer comprising palladium deposited on a support; (c) a second catalytic layer deposited onto the first catalytic layer, the second layer comprising the rhodium catalyst deposited on a support.
    [0039] In some embodiments, the front of the catalyst composite overlaps the rear of the catalyst composite. In some embodiments, the front part of the catalyst composite comprises between about 10 to 90%, more preferably about 20 to 60% and most preferably about 25 to 50% of the total length (for example, 1 to 15 cm in length total) of the substrate, such as a beehive substrate. In some embodiments, the rear part of the catalyst composite comprises between about 10 to 90%, more preferably about 40 to 80% and most preferably about 50 to 75% of the total length of the substrate, such as a honeycomb substrate.
    [0040] In some embodiments, one or more catalyst composites of the invention are arranged on a substrate. The substrate can be any of those materials typically used for the preparation of catalysts and will preferably comprise a ceramic or metal honeycomb structure. Any suitable substrate can be employed, such as a monolithic substrate of the type that has thin, parallel gas flow passages extending from there through a substrate inlet or outlet face, such that the passages are opened for the fluid to flow through (referred to as substrates that flow through a hive). The passages, which are essentially linear pathways from its fluid inlet to its fluid outlet, are defined by the walls on which the catalytic material is coated as a washcoat so that the gases flowing through the passages contact the catalytic material. The flow passages of the monolithic substrate are thin-walled channels, which can be of any shape and transverse size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures may contain between about 60 to 900 or more openings for inlet gas (i.e., cells) per square inch of cross section.
    [0041] The substrate can also be a wall flow filter, where the channels are alternately blocked, allowing gaseous flow to enter the channels from one direction (inlet direction) to flow through the channel walls and out through the channels through other direction (exit direction). A double oxidation catalyst composition can be coated on the wall flow filter. If such a substrate is used, the resulting system will be able to remove particulate matter along with gaseous pollutants. The substrate of the wall flow filter can be made from materials commonly known in the art, such as cordierite or silicon carbide. In some embodiments, the catalyst composite of the present invention shows a front region comprising 1 st and 2 nd deposited catalytic layers over the input channels of the wall flow filter and back portion comprising 1 st and 2 nd layers catalytic deposited on the inlet channels of a stop flow filter.
    [0042] In some embodiments, where the anterior to posterior zones are coated on separate bricks , the anterior zone can be a wall flow filter substrate and the posterior zone can be a flow hive substrate. In some embodiments, the anterior zone is a drainage hollow substrate and the posterior zone is coated over a wall flow filter element.
    [0043] Ceramic substrates can be made of any suitable refractory material, for example, cordierite, cordierite-alumina, silicon nitrite, mullite zirconia, spodumene, magnesium alumina-silica, zirconia silicate, silimanite, a magnesium silicate, zirconia, petalite, alumina, an aluminum silicate and the like.
    [0044] The substrates useful for the catalyst composite of the present invention can also be metallic in nature and be composed of one or more metals or metal alloys. Metal substrates can be used in various forms such as a corrugated sheet or a monolithic form. Preferred 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 can contain one or more of nickel, chromium and / or aluminum and the total amount of these metals can advantageously comprise at least about 15% by weight of the alloy, for example, about 10 to 25% by weight of chromium, about from 3 to 8% by weight of aluminum and up to about 20% by weight of nickel. The alloys can 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 substrates can be oxidized at high temperatures, for example about 1000 ° C or more, to improve the corrosion resistance of the alloys by forming an oxide layer on the substrate surfaces. Such high temperature-induced oxidation can enhance the adhesion of the refractory metal oxide support and catalytically promoting metal components to the substrate. In alternative embodiments, one or more catalyst compositions can be deposited on an open cell foam substrate. Such substrates are well known in the art and are typically formed from refractory ceramic or metallic materials.
    [0045] Based on the prior art, the configuration of the WC composition of the present invention is not taught or recognized as having favorable performance or other beneficial characteristics. In fact, the prior art teaches against this configuration as outlined in detail in the patent by Hu et al., And its references. PREPARATION:
    [0046] The stratified catalyst composite of the present invention can be easily prepared by processes known in the art. See, for example, US6478874 and EP0441173, which are incorporated herein by reference in their entirety. A representative process is described below. As used here, the term "washcoat '" has its common meaning in the technique of a thin, sticky coating of a catalytic material or other material applied on a substrate material, such as a honeycomb substrate member, which is sufficiently porous to allow passage of the gas flow to be treated.
    [0047] The catalyst composite can easily be prepared in layers on a monolithic substrate. For a first layer of a specific washcoat , finely divided particles of a large surface area refractory metal oxide such as gamma-alumina are suspended in an appropriate solvent, for example, water. The substrate can then be immersed one or more times in such a suspension or the suspension can be coated on the substrate, such that the desired loading of metal oxide is deposited on the substrate, for example, 0.5 to 2.5 g / in 3 . To incorporate components such as precious metals (for example, palladium, rhodium, platinum and / or combinations thereof), stabilizers, binders, additives and / or promoters, such components can be incorporated into the suspension as a mixture of compounds or complexes soluble in water or dispersed in water. Then, the coated substrate is calcined by heating, for example, at about 300 to 800 ° C for about 1 to 3 hours. Typically, when palladium is desired, the palladium component is used in the form of a compound or complex to obtain a high dispersion of the component on the refractory metal oxide support, for example, activated alumina. For the purposes of the present invention, the term "palladium component" means any compound, complex or the like that after calcination or use, decomposes or otherwise converts to a catalytically active form, usually metal or metal oxide. Soluble compounds in water or compounds or complexes dispersed in the water of the metal component may be used, provided that the liquid medium used to impregnate or deposit the metal component on particles the refractory metal oxide support does not react adversely with the metal or its compound or its complex or other components that may be present in the catalyst composite and is capable of being removed from the metal compound by volatilization or decomposition after heating under vacuum. In some cases, complete removal of the liquid may not occur until that the catalyst is put into use and subjected to high temperatures encountered during operation. Generally, from the aspect point of view the economical and environmental, aqueous solutions of soluble compounds or complexes of precious metals are used. For example, suitable compounds are palladium nitrate or rhodium nitrate. During the calcination step or at least during the initial use phase of the composite, such compounds are converted to a catalytically active form of the metal or a compound thereof.
    [0048] In some embodiments, the slurry is crushed to result in substantially all solids having particle sizes of less than 20 microns, that is, between about 0.1 to 15 microns, of average diameter. The combination can be obtained in a ball mill or other similar equipment and the solids content of the suspension can be, for example, about 15 to 60% by weight, more particularly about 25 to 40% by weight.
    [0049] Additional layers may be prepared and deposited after the first (1 a) catalytic layer in the same manner as described above for depositing the first (1 a) catalytic layer on the substrate.
    [0050] Before describing various exemplary embodiments of the invention, it should be understood that the invention is not limited to the details of construction or process steps described in the description below. The invention is capable of other modalities and of being practiced in several ways. MODES OF CATALYTIC LAYER 1 to FORMER
    [0051] According to some embodiments, the first layer that is deposited on, that is, coated on and adhered to the substrate comprises palladium deposited on a support. A suitable support is a refractory metal oxide with a large surface area. In a specific embodiment, the loading of the first layer on the substrate is between about 0.2 to 2.8 g / in 3 . Examples of large surface area refractory metal oxides include, but are not limited to, alumina, silica, titanium and zirconia and mixtures thereof. Refractory metal oxide may consist of or contain a mixed oxide such as silica-alumina, alumina-silicates which may be amorphous or crystalline, alumina-zirconia, alumina-lanthanum, alumina-barium-lanthanum-neodymium, alumina-chromium, alumina- barium, cerium-alumina and the like. An exemplary refractory metal oxide comprises gamma-alumina which has a specific area of about 50 to 350 m 2 / g which is present in a loading of about 10 to 90% by weight of the washcoat. The first layer will typically have oxygen storage components in the range of about 10 to 90% by weight with a cerium content ranging from about 3 to 98% by weight of the layer material.
    [0052] Examples of loading palladium on the first layer include up to about 15% by weight, alternatively between about 0.05 and about 10% by weight of palladium. This layer can also contain up to about 40% of stabilizers / promoters / binders / additives. Suitable stabilizers include one or more non-reducible metal oxides in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium and mixtures thereof. In some embodiments, the stabilizer comprises one or more oxides of barium and / or strontium. Suitable promoters include one or more non-reducible oxides or rare earth and transition metals selected from the group consisting of lanthanum, neodymium, praseodymium, yttrium, zirconia, samarium, gadolinium, dysprosium, ytterbium, niobium and their mixtures. TERMS OF CATALYTIC LAYER 2 to PREVIOUS AND SUBSEQUENT
    [0053] A second catalytic layer, which is deposited upon, i.e., coated upon and adhered to one the previous catalytic layer comprises rhodium or rhodium and deposited platinum on the refractory metal oxide of large surface area and / or oxygen storage component which can be any one of those mentioned above regarding the catalysts 1-optic layer. The second catalytic layer is present at a loading of about 0.2 to 2.8 g / in 3 alternatively between about 1 to 1.6 g / in 3 and have substantially an amount of oxygen storage component in a load of about 10 to 90% by weight. The oxygen storage components can be a cerium / zirconia composite containing cerium with cerium in the range of about 3 to 90% by weight. Preferably, about 5 to 55% cerium by weight is in the composite. The second catalytic layer may also comprise gamma alumina or stabilized gamma alumina having a specific surface area of 50 350 m 2 / g and which is present in a loading of about 10 to 90% by weight.
    [0054] In some embodiments, the rhodium is present in the second catalytic layer at a loading of about 0.01 to 1.0 wt%, alternatively from about 0.05 - 0.5% ; by weight of rhodium, preferably about 0 , 1 - 0.25% rhodium by weight. In some embodiments, the palladium is present in the second catalytic layer at a loading of about 0.1 - 10% by weight, alternatively about 0.1 to 5.0% by weight of palladium, preferably about 0.2 - 2.0% by weight of palladium. In some embodiments, platinum will be present in the catalytic layer in a loading of about 0.01 - 2.0% by weight, alternatively about 0.05 - 1.0% by weight of platinum, preferably about 0, 1 - 0.5% by weight of platinum. The second catalytic layer can also contain about 0 - 40% by weight of a promoter. Suitable promoters include one or more base metal oxides in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium, one or more rare-earth and transition metals selected from the group consisting of zirconia, lanthanum, praseodymium, yttrium, samarium, gadolinium, dysprosium, ytterbium, niobium, neodymium and mixtures of these. MODES OF LAYER 1 to catalytic post
    [0055] According to some embodiments, the first subsequent catalytic layer that is deposited onto, i.e. attached and coated on the substrate comprises palladium deposited on a support. A suitable support is a refractory metal oxide with a large surface area. In a specific embodiment, the loading of the first layer on the substrate is between about 0.2 to 2.8 g / in 3 . Examples of large surface area refractory metal oxides include, but are not limited to, alumina, silica, titanium and zirconia and mixtures thereof. Refractory metal oxide may consist of or comprise a mixed oxide such as silica-alumina, alumina-silicates which may be amorphous or crystalline, alumina-zirconia, alumina-lanthanum, alumina-barium-lanthanum-neodymium, alumina-chromium, alumina- barium and the like. An exemplary refractory metal oxide comprises gamma-alumina which has a specific area of about 50 to 350 m 2 / g which is present in a loading of about 0.5 to 2.8 g / in 3 . The first that is applied to the posterior zone is free of oxygen storage materials that comprise cerium.
    [0056] Examples of loading palladium on the first layer include up to about 15% by weight, alternatively between about 0.05 and about 10% by weight of palladium. This layer can also contain up to about 40% of stabilizers / promoters / binders / additives. Suitable stabilizers include one or more non-reducible metal oxides in which the metal is selected from the group consisting of barium, calcium, magnesium, strontium and mixtures thereof. In some embodiments, the stabilizer comprises one or more oxides of barium and / or strontium. Suitable promoters include one or more non-reducible oxides or rare earth and transition metals selected from the group consisting of lanthanum, neodymium, praseodymium, yttrium, zirconia, samarium, gadolinium, dysprosium, ytterbium, niobium and their mixtures. Examples:
    [0057] This invention will be illustrated by the following examples and descriptions. The following examples are intended to illustrate, but not to limit the invention. The configurations of the WC composition for a conventional reference catalyst (figure 4a) and a catalyst according to the present invention (figure 4b) were manufactured and compared as follows, MANUFACTURE OF CATALYTIC first layer CONVENTIONAL REFERENCE CATALYST (4a):
    [0058] The preparation of the washcoats and the coating has been previously described in US7041622, column 9, lines 20 to 40, column 10, lines 1 to 15, which is hereby incorporated by reference in its entirety. Alumina stabilized with 4% by weight of lanthanum oxide, barium sulfate and a mixed oxide oxygen storage material with a composition of 42% ZrO 2 + HfO 2 , 43% CeO 2 , 5% Pr 5 Or and 10% La 2 O 3 , by weight, was used in the preparation of the slurry. When making the catalysts in layers, a slurry was prepared by first adding nitric acid to water at 1% by weight, based on the total solids in the slurry, BaSO 4 was then added with stirring followed by the OSC. The slurry was stirred for 15 minutes and then the alumina was added slowly and stirred for 30 minutes. The slurry was then crushed (using a Sweco type mill) so that the ad 50 was 4.5 to 5.5 microns, the d50 was 17 to 21 microns, and 100% of the passage was less than 65 microns (that is, 100% of the particles were smaller than 65 micrometers in size). The slurry was then weighed and the LOI (loss on ignition) was measured at 540 C to determine the content of total calcined solids. Based on this value, the weight of the required Pd solution was calculated, a Pd nitrate solution was then added to the slurry with stirring drip. After the addition of Pd, the specific gravity of the slurry was in the range of 1.49 to 1.52, parts were coated by immersing one end of a ceramic hive monolith in the washcoat aqueous slurry, followed by extraction of the slurry to the channels using vacuum. The part was then removed from the slurry and the channels cleaned by applying vacuum to the other end of the part. Washcoat loading was controlled by varying specific gravity, and other coating parameters such as vacuum time and the amount of slurry extracted into the hive channels. After applying the washcoat, the parts were calcined at 540 ° C for 2 hours. After calcination the composition of the first catalyst layer was as follows: 56,5g / l of lanthanum stabilized alumina; 36.5 g / l of oxygen storage material; 16.5 g / l barium sulfate; and 0.635 g / l palladium, MANUFACTURING 2 to LAYER CATALYTIC OF CONVENTIONAL REFERENCE CATALYST:
    [0059] The second catalytic layer of the conventional reference catalyst consisted of stabilized alumina containing 4% by weight of lanthanum oxide, barium sulfate and a mixed oxide oxygen storage material having a composition of 58% ZrO 2 + HfO 2 , 32% CeO 2 , 8% Y 2 O 3 and 2% La 2 O 3 . The slurry was prepared as described above for the previous first catalytic layer. Rh was added to the aqueous slurry over a period of 30 minutes with stirring. After coating and calcining at 540 ° C for 2 hours, the composition of the previous 2nd catalyst layer of the catalyst was as follows: 61 g / l of alumina stabilized with lanthanum; 61.5 g / l of oxygen storage material; 1.65 g / l barium sulfate; and 0.071 g / l rhodium. MANUFACTURING 2 to LAYER CATALYTIC AGREEMENT CATALYST BACK WITH THE INVENTION:
    [0060] The composition and fabrication of the subsequent second catalytic layer were identical to those of the standard reference catalyst. MANUFACTURING 1 to CATALYTIC LAYER OF THE AGREEMENT OF CATALYST BACK WITH THE INVENTION:
    [0061] The first catalytic layer to subsequent consisted of alumina stabilized with 4% by weight lanthanum oxide and barium sulfate. The slurry was prepared as described above for the previous first catalytic layer. After calcination at 540 ° C for 2 hours, the composition of the first catalytic layer later was as follows: 73.0 g / l of alumina stabilized with lanthanum; 21.0 g / l barium sulfate; and 0.635 g / l palladium.
    [0062] As noted above, the same oxygen storage material was used in the Rh layer of the conventional uniform design reference and zoned design according to the invention, where the first subsequent catalytic layer of the rear region does not contain a storage material oxygen. The reference catalyst in the current case consisted of a 15.24 cm (6 '') long monolith while the test system consisted of a 7.62 cm (3 '') front brick with WC design and composition identical. The rear brick of 7.62 cm (3 '') was identical to the above except that the catalyst was removed from the OSC 1 subsequent catalytic layer and alumina / additional promoter was added in place to give a full charge to the toilet 1 the 1.8 g / in 3 layer. Both the 7.62 cm (3 ") front and rear bricks were joined in the converter to represent a zoned configuration.
    [0063] Aging consisted of 50 or 100 hours of a 4-way thermal aging protocol. The cycle consisted of four modes over a period of 60 seconds. The first mode consisted of a stoichiometric cruise, followed by a rich condition, a rich condition with secondary air injection and finally a stoichiometric condition with secondary air injection. Mode 1 lasted 40 seconds with an inlet catalytic bed T (thermocouples placed 2.54 cm (1 ") from the inner face of the catalyst) of 904 ± 2 ° C. Mode 2 lasted 6 seconds with a concentration of 4.0 ± 0.1% CO catalyst inlet Mode 3 lasted 10 seconds with a 980 ° C ± 2 ° C inlet catalytic bed, the CO concentration outside the engine was 4.0 ± 0 , 1 vol% and a secondary air injection at the catalyst inlet was used to give an O 2 concentration of 2.5 ± 0.1 vol%. Mode 4 lasted 4 seconds with a stoichiometric exhaust gas composition outside the engine and secondary air injection to give an O 2 concentration of 4.5 ± 0.1 vol% at the catalyst inlet The engine used for aging was a 7.4L V-8 equipped with sequential multiport fuel injection.
    [0064] The performance results are summarized in Figures 5 and 6, where it is seen that the catalyst design of the present invention shows clear advantages for THC and NOx in Phases 2 and 3 of the FTP test.
    [0065] To the extent necessary to understand or complete the description of the present invention, all publications and patent applications mentioned herein are expressly incorporated by reference to the same extent as if each were individually incorporated.
    [0066] Having thus described the exemplary modalities of the present invention, it should be noted by those skilled in the art that the descriptions are only exemplary and that various other alternatives, adaptations and modifications can be made within the scope of the present invention. Consequently, the present invention is not limited to the specific modalities as illustrated herein, but is limited only by the following claims.
    权利要求:
    Claims (14)
    [0001]
    Catalytic composite for the purification of exhaust gases from a combustion engine that works substantially under stoichiometric conditions, characterized by the fact that it comprises in sequence and in order: a previous double-layer on a substrate having a first previous catalytic layer (bottom) and a catalytic layer 2 to the previous (higher); and a double backsheet on a substrate having a first subsequent catalytic layer (bottom) and a subsequent catalytic layer 2 (top); wherein 2 the anterior catalytic layer and 2 the posterior catalytic layer comprise rhodium as the platinum group metal compound; wherein 1 the anterior catalytic layer and 1 the posterior catalytic layer comprise palladium as the platinum group metal compound; wherein the first catalytic layer further comprises less than 1% of an oxygen storage component (OSC) by weight of the layer; and where the front double layer forms an anterior zone and the rear double layer forms a posterior zone where the catalyst composite is a single brick system or the anterior double layer is located on an anterior brick and the posterior double layer is located on a brick posterior where the catalyst composite is a multiple bricks system , in which the content of the oxygen storage component (OSC) by weight of the layers is as follows: 1 the previous catalytic layer - 10 to 80% by weight of the layer; 2 the anterior catalytic layer - 20 to 80% by weight of the layer; and 2 the posterior catalytic layer - 20 to 80% by weight of the layer.
    [0002]
    Composite catalyst according to claim 1, characterized by the fact that the above catalytic layer 2 and the second catalytic layer subsequent to establish a continuous layer.
    [0003]
    Catalyst composite according to claim 1, characterized by the fact that the PGM content of the layers is as follows: 1 the previous catalytic layer - 0.1 - 12.0% by weight of the layer; 1 the posterior catalytic layer - 0.01 - 6.0% by weight of the layer; 2 the previous catalytic layer - 0.01 - 2% by weight of the layer; and 2 the posterior catalytic layer - 0.01 - 2% by weight of the layer.
    [0004]
    Composite catalyst according to claim 1, characterized by the fact that the above catalytic layer 2 and / or the subsequent second catalytic layer comprising platinum.
    [0005]
    Catalyst composite according to claim 4, characterized by the fact that the platinum content of the layers is as follows: 2 the previous catalytic layer - 0.01 - 12.0% by weight of the layer; and 2 the posterior catalytic layer - 0.01 - 5.0% by weight of the layer.
    [0006]
    Catalyst composite according to claim 1, characterized by the fact that it additionally comprises exhaust treatment materials selected from the group consisting of HC storage and NOx storage catalysts, through which the HC and storage layer NOx storage is located as a bottom WC coating layer on the substrate to form an anterior zone or anterior brick and / or a posterior zone or posterior brick .
    [0007]
    Catalyst composite according to claim 1, characterized by the fact that it additionally comprises exhaust treatment materials selected from the group consisting of HC storage and NOx storage catalysts, through which the HC and storage layer NOx storage is located as the top layer or top layer of the WC layer to form an anterior zone or anterior brick and / or a posterior zone or posterior brick .
    [0008]
    Catalyst composite according to claim 1, characterized in that the catalyst composite is deposited, at least partially on an inner lining (UC) layer comprising a material selected from the group consisting of HC storage material or NOx storage.
    [0009]
    Catalyst composite according to claim 1, characterized in that the catalyst composite comprises an axial inlet end, axial outlet end, wall elements having an extension extending between the axial inlet end to the axial end of exit and a plurality of axially closed channels defined by the wall elements; wherein the first and second previous catalytic layers are deposited on the wall elements adjacent to the axial inlet end and having a length that extends less than the length of the wall of the wall elements to form a front region; and the 1 to 2 and the subsequent catalytic layers are deposited on the wall elements adjacent to the axial outlet end and having a length that extends less than the length of the wall elements to form a rear region.
    [0010]
    Composite catalyst according to claim 1, characterized by the fact that the 1 st and 2 nd previous catalytic layers are deposited on the input channels of a wall flow filter for forming the anterior and 1 st and 2 nd layers posterior catalysts are deposited on the outlet channels of a wall flow filter to form the posterior zone.
    [0011]
    Composite catalyst according to claim 1, characterized by the fact that the 1 st and 2 nd previous catalytic layers are deposited over the channels of a substrate in honeycomb fashion to form the anterior and 1 st and 2 nd catalytic layers posterior ones are deposited on the entrance and / or exit channels of a wall flow filter to form the posterior zone.
    [0012]
    Exhaust treatment system for the purification of exhaust gases from a combustion engine, characterized by the fact that it works substantially under stoichiometric conditions and that comprises the catalyst composite as defined in claim 1.
    [0013]
    Exhaust treatment system according to claim 12, characterized in that it additionally comprises one or more devices for exhaust treatment selected from the group consisting of HC capture and NOx storage catalyst.
    [0014]
    Method of treating exhaust gases from a combustion engine that functions substantially under stoichiometric conditions, characterized by the fact that it comprises: contacting a gaseous stream comprising hydrocarbons, carbon monoxide and nitrogen oxides with a catalyst composite as defined in claim 1 , in which the catalyst composite is effective to substantially simultaneously oxidize carbon monoxide and hydrocarbons and reduce nitrogen oxides.
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    同族专利:
    公开号 | 公开日
    EP2643078A1|2013-10-02|
    US20120128558A1|2012-05-24|
    RU2013128390A|2014-12-27|
    JP5841161B2|2016-01-13|
    EP2643078B1|2017-06-21|
    US20130058848A1|2013-03-07|
    BR112013011920A2|2017-11-14|
    WO2012069405A1|2012-05-31|
    JP2014509242A|2014-04-17|
    CN103201018B|2016-01-20|
    CN103201018A|2013-07-10|
    KR101913664B1|2018-11-01|
    KR20130141540A|2013-12-26|
    US8394348B1|2013-03-12|
    US8323599B2|2012-12-04|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-04-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/951,311|US8323599B2|2010-11-22|2010-11-22|Three-way catalyst having an upstream multi-layer catalyst|
    US12/951,311|2010-11-22|
    PCT/EP2011/070541|WO2012069405A1|2010-11-22|2011-11-21|Three-way catalytic system having an upstream multi - layer catalyst|
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